Production of Vinyl Terminated Polyethylene Using Supported Catalyst System

ABSTRACT

This invention relates to processes to produce vinyl terminated polyethylene involving contacting ethylene with a supported metallocene catalyst system; wherein the supported catalyst system comprises a support material; an alumoxane activator; and a metallocene compound. A supported metallocene catalyst system is also disclosed. Processes to produce ethylene copolymers are also disclosed.

CROSS REFERENCE TO PRIORITY APPLICATION

This application claims priority to and the benefit of U.S. ProvisionalApplication No. 61/704,606, filed Sep. 24, 2012, the disclosure of whichis incorporated herein by reference in its entirety.

STATEMENT OF RELATED CASES

This application relates to U.S. Provisional Application Ser. No.61/704,604, Attorney Docket No. 2012EM185, filed on Sep. 24, 2012; andU.S. Provisional Application Ser. No. 61/704,611, Attorney Docket No.2012EM064, filed on Sep. 24, 2012.

FIELD OF THE INVENTION

This invention relates to heterogeneous processes to produce vinylterminated polyethylene, particularly vinyl terminated ethylenehomopolymers and vinyl terminated ethylene copolymers.

BACKGROUND OF THE INVENTION

Polyolefins are the largest-volume family of commercially important,high tonnage thermoplastics and are produced by a worldwide industrywith impressive capacity. Even more impressive is the wide range ofpolymer types and grades that have been obtained from simple startingmaterials, such as ethylene and propylene. Polyethylene has the world'slargest market share among the polyolefins.

Modification of polyethylene is particularly attractive, because it mayallow enhancement of existing polyethylene properties and may evenconfer new properties that may extend application potential.Polyethylene may have a reactive moiety, for example, a vinyl orvinylidene group, that may allow the polyethylene to be functionalizedor to be used as macromonomers, allowing them to become furtherincorporated into another polymer chain. Vinyl groups tend to be morereactive than the more sterically crowded vinylidene groups. Vinylterminated polyethylenes are therefore desirable. Additionally,polyethylenes that have about one vinyl end group per polymer moleculeare even more desirable. If every polyethylene has a reactive moietycapable of being functionalized or otherwise modified, then there wouldbe appreciable cost savings and efficiency in using such a polyethylene.Accordingly, there is a need for vinyl terminated polyethylene,particularly vinyl terminated polyethylene having about one vinyl groupper polyethylene molecule.

U.S. Pat. No. 6,169,154 discloses a branched ethylenic macromonomer,derivable from ethylene singly or derivable from ethylene and anotherolefin, where (a) the molar ratio of a terminal methyl group/a vinylgroup is in the range of from 1 to 100, the macromonomer having a branchother than the branch directly derived from the other olefin; (b) aratio of vinyl groups to the total unsaturated groups in themacromonomer being 70 mol % or more; and (c) a weight average molecularweight of the macromonomer in terms of a polyethylene measured by a GPCbeing in the range of 100 to 20,000.

Huang et al. (Appl. Organometal. Chem. 2010, 24, 727-733) disclose thesynthesis of long-chain branched polyethylene including the generationof vinyl-terminated polyethylene macromonomers, using bridgedcyclopentadienyl indenyl(fluorenyl)zirconocenes. The vinyl-terminatedpolyethylene macromonomers were reported to have a Mn(NMR) in the rangeof 3300 to 10,300 g/mol and terminal vinyl percentages of 80.7% to94.9%.

JP 2012/116871 discloses catalysts for the polymerization of olefins andthe manufacture of olefin polymers with good particle shape. Thesecatalysts comprise (a) solid aluminoxanes; (b) organometallic compoundsof (b-1) AlR⁵ ₃ or (b-2) M³R⁵ ₂ (R⁵═H, halo, C₁₋₂₀ hydrocarbyl oralkoxy, C₆₋₂₀ aryloxy, M³=Mg, Zn); and (c) metallocenes of Group 4metals. Olefin polymers were manufactured by the polymerization ofethylene and comonomers using the catalysts. The catalysts were reportedto be useful for the manufacture of vinyl-terminated macromers. Thus,ethylene was polymerized in the presence of aluminoxane,dimethylsilylenebis(cyclopentadienyl)zirconium dichloride, andtriisobutylaluminum to give polyethylene reported to have a Mn of 11,500g/mol, molecular weight distribution of 2.4, and a selectivity ofterminal vinyl groups of 0.59.

JP 2008/050278 discloses silylene(cyclopentadienyl)(indenyl)transitionmetal (Ti, Zr, and Hf) compounds, olefin polymerization catalystscontaining them, and the manufacture of polyolefins. Polyolefins havingvinyl end groups, useful as macromonomers, were manufactured with thesecatalysts. In particular, ethylene was polymerized withdimethylsilylene(cyclopentadienyl)(2,4,7-trimethylindenyl)zirconiumdichloride, N,N-dimethyloctadecylamine HCl salt-treated hectorite,Et₃Al, and (iso-Bu)₃Al to give polyethylene reported to have vinyl endgroups of 0.07/1000 C atoms.

JP 2007/246433 discloses metallocenes with long hydrocarbyl-containingbridging groups, olefin polymerization catalysts containing them, andmanufacture of vinyl-terminated polyolefins. The metallocenes have thestructure I, below:

[M¹=Ti, Zr, Hf; X═H, halo, C₁₋₂₀ hydrocarbyl, etc.; Cp¹,Cp²=(substituted) cyclopentadienyl, (substituted) benzocyclopentadienyl,(substituted) dibenzocyclopentadienyl; substituent for Cp¹ and Cp²=halo,C₁₋₂₀ hydrocarbyl, C₁₋₂₀ alkoxy, etc.; R¹═C₁₋₄₀ hydrocarbyl; R²═C₂₁₋₄₀hydrocarbyl; Q=C, Si, Ge, Sn]. Ethylene was polymerized with I (R¹=Me,R²=docosyl, Q=Si, Cp¹=Cp²=cyclopentadienyl, M¹=Zr, X═Cl),N,N-dimethyloctadecylamine HCl salt-modified hectorite, and (iso-Pr)₃Alto give polyethylene reported to have a number of vinyl end groups of0.42/1000 C atoms.

JP 2007/169340 discloses ethylene polymerization in the presence of acatalyst containing (propane-1,3-diyl-biscyclopentadienyl)zirconiumdichloride, (iso-Bu)₃Al, and N,N-dimethyloctadecylaminehydrochloride-modified hectorite to give polyethylene reported to have anumber of vinyl end groups of 0.05/1000 C atoms.

EP 0 530 408 discloses vinyl-terminated olefin polymers, reported tohave an Mn of 300 to 500,000, manufactured by polymerization of C₂₋₃alkenes in the presence of a reaction product of a polymerizationcatalyst consisting of a V chelate compound and a dialkylaluminum halidewith CH₂:CH(CmH₂m)CH:CH₂ (I, m=1-15), and then reacting with I and aproton donor. Polyethylene, reported to have an Mn of 300 to 300,000 andterminal groups COX[X═OH, OR₁, halogen, SO₃R₂; R₁═C1⁻⁵ alkyl;R₂=(un)substituted C₁₋₂₀ hydrocarbyl], is obtained by polymerization ofC₂H₄ in the presence of a dilithio compound amine complex, followed by areaction with CO₂, and a proton donor or sulfonyl halide. Thus,vinyl-terminated ethylene polymer was prepared by polymerization of C₂H₄in the presence of Et₂AlCl (where Et means ethyl),tris(2-methyl-1,3-butanedionato)vanadium, and 1,7-octadiene; forstructure proof it was refluxed with a solution of diborane in THF andBu₂O, and treated with aqueous NaOH containing H₂O₂. The OH-terminatedpolymer was then treated with Me₃SiCl in pyridine to givetrimethylsiloxy group-terminated polyethylene.

Britovsek et al. (J. Am. Chem. Soc. 1999, 121, 8728-8740) discloses thesynthesis, characterization, and ethylene polymerization behavior of aseries of iron and cobalt halide complexes, LMXn (M=Fe, X═Cl, n=2, 3,X═Br, n=2, M=Co, X═Cl, n=2) bearing chelating 2,6-bis(imino)pyridylligands L [L=2,6-(ArNCR¹)₂C₅H₃N]. X-ray diffraction studies showed thegeometry at the metal centers to be either distorted square pyramidal ordistorted trigonal bipyramidal. Treatment of the complexes LMX₁, withmethylaluminoxane (MAO) led to highly active ethylene polymerizationcatalysts converting ethylene to highly linear polyethylene (PE). LFeX₂precatalysts with ketimine ligands (R¹=Me) are approximately an order ofmagnitude more active than precatalysts with aldimine ligands (R¹═H).Catalyst productivities in the range 3,750 to 20,600 g/mmol·h·bar wereobserved for Fe-based ketimine catalysts, while Co ketimine systemsdisplayed activities of 450 to 1740 g/mmol·h·bar. Molecular weights(M_(w)) of the polymers produced were in the range 14,000 to 611,000.Changing reaction conditions also affected productivity and molecularweight; in some systems, a bimodal molecular weight distribution wasobserved.

However, few processes have been shown to produce a high percentage ofvinyl chain ends, in high yields, with a wide range of molecular weight,and with high catalyst activity for ethylene-based polymerizations,especially ethylene-based polymerizations catalyzed by a supportedcatalyst system. Accordingly, there is a need for new processes usingsupported catalyst systems that produce polyethylene polymers having ahigh percentage of vinyl chain ends, in high yields, with a wide rangeof molecular weight, with a narrow molecular weight distribution, andwith high catalyst activity. Further, there is a need for ethylene-basedreactive materials having vinyl chain ends which can be functionalizedand used in other applications.

SUMMARY OF THE INVENTION

The invention relates to a process to produce polyethylene comprising:

(a) contacting ethylene with a supported metallocene catalyst system;wherein the supported catalyst system comprises:

(i) a support material;

(ii) an alumoxane activator having from about 1 wt % to about 14 wt %trimethylaluminum, based on the weight of the alumoxane activator;

(iii) a metallocene compound represented by the formula:

wherein:

T is Si or Ge;

each R^(A) is a C₁ to C₂₀ substituted or unsubstituted hydrocarbylgroup;

each R^(B) is, independently, H, or a C₁ to C₈ substituted orunsubstituted hydrocarbyl group, or a group represented by the formula—CH₂R^(x);

wherein R^(x) is a C₁ to C₂₀ substituted or unsubstituted hydrocarbylgroup, provided that at least one R^(B) is methyl or a group representedby the formula —CH₂R^(x);

each R^(C) is, independently, H or a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl group;

each A is independently selected from the group consisting of C₁ to C₂₀substituted or unsubstituted hydrocarbyl groups, hydrides, amides,amines, alkoxides, sulfides, phosphides, halides, dienes, phosphines,and ethers, and two A groups can form a cyclic structure includingaromatic, partially saturated, or saturated cyclic or fused ring system;

each X is, independently, hydrogen, halogen or a substituted orunsubstituted C₁ to C₂₀ hydrocarbyl, and two X groups can form a cyclicstructure including aromatic, partially saturated, or saturated cyclicor fused ring system;

further provided that any of adjacent R^(A), R^(B), and/or R^(C) groupsmay form a fused ring or multicenter fused ring systems, where the ringsmay be substituted or unsubstituted, and may be aromatic, partiallyunsaturated, or unsaturated;

(b) obtaining a vinyl terminated polyethylene having:

(i) at least 60% allyl chain ends, based on the total unsaturations;

(ii) a molecular weight distribution of less than or equal to 4.0; and

(iii) a Mn (¹HNMR) of at least 20,000 g/mol.

This invention also relates to a supported catalyst system comprising:

(i) a support material;

(ii) an alumoxane activator having from about 1 wt % to about 14 wt %trimethylaluminum, based on the weight of the alumoxane activator; and

(iii) a metallocene compound represented by the formula:

wherein:

T is Si or Ge;

each R^(A) is a C₁ to C₂₀ substituted or unsubstituted hydrocarbylgroup;

each R^(B) is, independently, H or a C₁ to C₈ substituted orunsubstituted hydrocarbyl group, or a group represented by the formula—CH₂R^(x);

wherein R^(x) is a C₁ to C₂₀ substituted or unsubstituted hydrocarbylgroup, provided that at least one R^(B) is methyl or a group representedby the formula —CH₂R^(x);

each R^(C) is, independently, H or a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl group;

each A is independently selected from the group consisting of C₁ to C₂₀substituted or unsubstituted hydrocarbyl groups, hydrides, amides,amines, alkoxides, sulfides, phosphides, halides, dienes, phosphines,and ethers, and two A groups can form a cyclic structure includingaromatic, partially saturated, or saturated cyclic or fused ring system;

each X is, independently, hydrogen, halogen, or a substituted orunsubstituted C₁ to C₂₀ hydrocarbyl, and two X groups can form a cyclicstructure including aromatic, partially saturated or saturated cyclic orfused ring system; and

further provided that any of adjacent R^(A), R^(B), and/or R^(C) groupsmay form a fused ring or multicenter fused ring systems, where the ringsmay be substituted or unsubstituted, and may be aromatic, partiallyunsaturated, or unsaturated.

This invention also relates to a vinyl terminated polyethylene having:(a) at least 60% allyl chain ends, based on the total unsaturations; (b)a molecular weight distribution of less than or equal to 4.0; (c) ag′(vis) of greater than 0.95; and (d) an Mn (¹HNMR) of at least 20,000g/mol.

This invention also relates to reaction products of the vinyl terminatedpolyethylene and a modifying agent, wherein the reaction product is afunctionalized polyethylene having: (i) at least 50% modified groups;(ii) a molecular weight distribution of less than or equal to 4.0; and(iii) a g′(vis) of 0.95 or less.

This invention also relates to an article comprising the vinylterminated polyethylene and/or the functionalized polyethylene.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of the branching index, g′(vis) versus the hexene (C₆)content of the ethylene copolymers of Example 1.

DETAILED DESCRIPTION

Polyethylenes with high percentage of allyl chain ends may be producedusing supported non-metallocene catalysts comprising metals such as Crand Fe. However, the molecular weight distribution (MWD) of thesepolyethylenes is typically very broad. Using supported metallocenecompounds may produce more narrow MWD polyethylenes, but very fewsupported metallocene compounds have been shown to yield a highpercentage of allyl chain ends. The parity between number averagemolecular weight obtained from GPC data and that obtained by NMR data ispoor which generally indicates that large amounts of doubly saturatedpolyethylene chains are produced. Additionally, although polyethyleneshaving a high percentage of allyl chain ends may be made fromunsupported metallocene compounds and non-coordinating anion activators,processes using unsupported metallocene compounds typically result inreactor fouling. Allyl chain ends are reported as a molar percentage ofthe total number of moles of unsaturated groups (that is, the sum ofallyl chain ends, vinylidene chain ends, vinylene chain ends, and thelike).

The inventors have advantageously found that through the selection of ametallocene compound ligand, a metallocene compound metal and/ormodification of an alumoxane activator of a supported metallocenecompound that polyethylenes having high percentages of allyl chain endsmay be produced without reactor fouling. The polyethylene is composed ofdiscrete particles and is free flowing.

DEFINITIONS

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as in CHEMICALAND ENGINEERING NEWS, 63(5), 27 (1985). Therefore, a “Group 4 metal” isan element from Group 4 of the Periodic Table.

“Catalyst productivity” is a measure of how many grams of polymer (P)are produced using a polymerization catalyst comprising W g of catalyst(cat), over a period of time of T hours; and may be expressed by thefollowing formula: P/(T×W) and expressed in units of gP/gcat/hr.“Catalyst activity” is a measure of how many grams of polymer of polymerare produced using a polymerization catalyst comprising W g of catalyst(cat) and may be expressed by the following formula: P/W and expressedin units of gP/g(cat), and is typically used for batch processes.Catalyst activity may be converted to catalyst productivity by takinginto account the run time of the batch process: catalystproductivity=catalyst activity/T, where T is the run time in hours.

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For the purposes of this invention and the claims thereto,when a polymer is referred to as “comprising an olefin,” the olefinpresent in the polymer is the polymerized form of the olefin. Forexample, when a copolymer is said to have an “ethylene” content of 35 wt% to 55 wt %, it is understood that the mer unit in the copolymer isderived from ethylene in the polymerization reaction and said derivedunits are present at 35 wt % to 55 wt %, based upon the weight of thecopolymer. A “polymer” has two or more of the same or different merunits. “Polymer,” as used herein, includes oligomers (up to 100 merunits) and larger polymers (greater than 100 mer units).

A “homopolymer” is a polymer having mer units that are the same. A“copolymer” is a polymer having two or more mer units that are differentfrom each other. A “terpolymer” is a polymer having three mer units thatare different from each other. “Different,” as used to refer to merunits, indicates that the mer units differ from each other by at leastone atom or are different isomerically. Accordingly, the definition ofcopolymer, as used herein, includes terpolymers and the like.

As used herein, “molecular weight” means number average molecular weight(Mn), unless otherwise stated. As used herein, Mn is number averagemolecular weight (measured by ¹H NMR, unless stated otherwise), Mw isweight average molecular weight (measured by Gel PermeationChromatography, GPC), and Mz is z average molecular weight (measured byGPC), wt % is weight percent, mol % is mole percent, vol % is volumepercent, and mol is mole. Molecular weight distribution (MWD) is definedto be Mw (measured by GPC) divided by Mn (measured by GPC), Mw/Mn.

Mn (¹H NMR) is determined according to the NMR methods described below.Mn(GPC) is determined using the GPC method, as described below. For thepurpose of the claims, unless otherwise stated, Mn is determined by ¹HNMR. Unless otherwise noted, all molecular weights (e.g., Mw, Mn, Mz)have units of g/mol.

The unsaturated chain end of inventive polyethylenes comprises an “allylchain end.” An “allyl chain end” is represented by CH₂CH—CH₂—, as shownin the formula:

where M_(p) represents the polymer chain. “Vinyl terminated,” asreferred to throughout means having an allyl chain end. Preferably, theinventive polyethylenes also have a saturated chain end.

Supported Metallocene Catalyst System

This invention relates to a supported catalyst system comprising:

(i) a support material (preferably Al₂O₃, ZrO₂, SiO₂, and combinationsthereof, more preferably SiO₂, Al₂O₃, or SiO₂/Al₂O₃);(ii) an alumoxane activator having from about 1 wt % to about 14 wt %trimethylaluminum (preferably less than 13 wt %, preferably less than 12wt %, preferably less than 10 wt %, preferably less than 5 wt %, or 0 wt%, or, optionally, greater than 0 wt %, or greater than 1 wt %), basedon the weight of the alumoxane activator; and(iii) a metallocene compound represented by the formula:

wherein:

T is Si or Ge (preferably T is Si);

each R^(A) is a C₁ to C₂₀ substituted or unsubstituted hydrocarbyl group(preferably R^(A) is methyl or ethyl; preferably methyl);

each R^(B) is, independently, H or a C₁ to C₈ substituted orunsubstituted hydrocarbyl group, or a group represented by the formula—CH₂R^(x) (preferably R^(B) is methyl, n-propyl, n-butyl, benzyl,sec-butyl, or —CH₂-cyclopropyl);

wherein R^(x) is a C₁ to C₂₀ substituted or unsubstituted hydrocarbylgroup, provided that at least one R^(B) is methyl or a group representedby the formula —CH₂R^(x) (preferably —CH₂R^(x) is one of n-propyl,n-butyl, sec-butyl, —CH₂-cyclopropyl, or benzyl groups);

each R^(C) is, independently, H or a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl group (preferably R^(C) is H);

each A is independently selected from the group consisting of C₁ to C₂₀substituted or unsubstituted hydrocarbyl groups, hydrides, amides,amines, alkoxides, sulfides, phosphides, halides, dienes, phosphines,and ethers (preferably A is Cl or methyl), and two A groups can form acyclic structure including aromatic, partially saturated, or saturatedcyclic or fused ring system;

each X is, independently, hydrogen, halogen or a substituted orunsubstituted C₁ to C₂₀ hydrocarbyl, and two X groups can form a cyclicstructure including aromatic, partially saturated, or saturated cyclicor fused ring system (preferably X is methyl, ethyl, hexyl,silacyclobutyl, or silacyclopentyl);

further provided that any of adjacent R^(A), R^(B), and/or R^(C) groupsmay form a fused ring or multicenter fused ring systems, where the ringsmay be substituted or unsubstituted, and may be aromatic, partiallyunsaturated, or unsaturated (preferably R^(B) and/or R^(A) or R^(C) fuseto form a substituted or unsubstituted indene or a fluorene; preferablythe metallocene compound is not a bis-fluorenyl compound); and(iv) optionally, at least one cocatalyst (or scavenger) (preferably oneor more of triethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diethyl aluminum chloride, dibutyl zinc, diethylzinc, and the like).

The supported metallocene catalyst system of this invention comprises asupport material, an alumoxane activator, a metallocene compound, and anoptional cocatalyst/scavenger, each of which is discussed in turn below.

Support Material

In embodiments of the invention herein, the catalyst system comprises aninert support material. Preferably, the supported material is a poroussupport material, for example, talc, and inorganic oxides. Other supportmaterials include zeolites, clays, organoclays, or any other organic orinorganic support material, or mixtures thereof.

Preferably, the support material is an inorganic oxide in a finelydivided form. Suitable inorganic oxide materials for use in metallocenecatalyst systems herein include Groups 2, 4, 13, and 14 metal oxidessuch as silica, alumina, and mixtures thereof. Other inorganic oxidesthat may be employed, either alone or in combination, with the silica oralumina are magnesia, titania, zirconia, and the like. Other suitablesupport materials, however, can be employed, for example, finely dividedfunctionalized polyolefins such as finely divided polyethylene.Particularly useful supports include magnesia, titania, zirconia,montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.Also, combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania, and the like. Preferredsupport materials include Al₂O₃, ZrO₂, SiO₂, and combinations thereof,more preferably SiO₂, Al₂O₃, or SiO₂/Al₂O₃.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 m²/g to about700 m²/g, pore volume in the range of from about 0.1 cc/g to about 4.0cc/g, and average particle size in the range of from about 5 μm to about500 μm. More preferably, the surface area of the support material is inthe range of from about 50 m²/g to about 500 m²/g, pore volume of fromabout 0.5 cc/g to about 3.5 cc/g, and average particle size of fromabout 10 μm to about 200 μm. Most preferably, the surface area of thesupport material is in the range is from about 100 m²/g to about 400m²/g, pore volume from about 0.8 cc/g to about 3.0 cc/g, and averageparticle size is from about 5 μm to about 100 μm. The average pore sizeof the support material useful in the invention is in the range of from10 to 1000 Å, preferably 50 to about 500 Å, and most preferably 75 toabout 350 Å. In some embodiments, the support material is a high surfacearea, amorphous silica (surface area ≧300 m²/gm, pore volume ≧1.65cm³/gm), and is marketed under the tradenames of DAVISON 952 or DAVISON955 by the Davison Chemical Division of W. R. Grace and Company, areparticularly useful. In other embodiments, DAVIDSON 948 is used.

In some embodiments of this invention, the support material may be dry,that is, free of absorbed water. Drying of the support material can beachieved by heating or calcining at about 100° C. to about 1000° C.,preferably at least about 600° C. When the support material is silica,it is typically heated to at least 200° C., preferably about 200° C. toabout 850° C., and most preferably at about 600° C.; and for a time ofabout 1 minute to about 100 hours, from about 12 hours to about 72hours, or from about 24 hours to about 60 hours. The calcined supportmaterial preferably has at least some reactive hydroxyl (OH) groups.

Alumoxane Activators

The term “activator” is used herein to be any compound which canactivate any one of the metallocene compounds described above byconverting the neutral catalyst compound to a catalytically activemetallocene compound cation. Preferred activators typically includealumoxane compounds (or “alumoxanes”) and modified alumoxane compounds.

Alumoxanes are generally oligomeric compounds containing —Al(R¹)—O—sub-units, where R¹ is an alkyl group. Examples of alumoxanes includemethylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane,isobutylalumoxane, and mixtures thereof. Alkylalumoxanes and modifiedalkylalumoxanes are suitable as catalyst activators, particularly whenthe abstractable ligand is an alkyl, halide, alkoxide, or amide.Mixtures of different alumoxanes and modified alumoxanes may also beused. It may be preferable to use a visually clear methylalumoxane. Acloudy or gelled alumoxane can be filtered to produce a clear solutionor clear alumoxane can be decanted from the cloudy solution. Anotheruseful alumoxane is a modified methylalumoxane (MMAO) cocatalyst type 3A(commercially available from Akzo Chemicals, Inc. under the trade nameModified Methylalumoxane type 3A, covered under U.S. Pat. No.5,041,584). In preferred embodiments of this invention, the activator isan alkylalumoxane, preferably methylalumoxane or isobutylalumoxane.

In preferred embodiments of this invention, the alumoxane activator is aTMA-depleted activator (where TMA means trimethylaluminum). Theinventors have advantageously found that using a TMA-depletedalkylalumoxane contributes to producing a polymer with higher allylchain ends. Commercial alumoxanes, such as methylalumoxane (MAO) andmodified MAO, and mixtures of other of those with another alumoxane, forexample isobutylalumoxane, often tend to comprise some residualtrimethylaluminum as an impurity. For example, one common method ofmaking MAO is the hydrolysis of trimethylaluminum (TMA). Suchhydrolysis, however, tends to leave residual TMA in the MAO which mayhave negative effects on polymerization. Any methods known in the art toremove TMA may be used. For example, to produce a TMA-depleted alumoxaneactivator, a solution of alumoxane (such as methylalumoxane), forexample, 30 wt % in toluene may be diluted in toluene and the aluminumalkyl (such as TMA in the case of MAO) is removed from the solution, forexample, by combination with trimethylphenol and filtration of thesolid.

In such embodiments, the TMA-depleted alumoxane activator comprises fromabout 1 wt % to about 14 wt % trimethylaluminum (preferably less than 13wt %, preferably less than 12 wt %, preferably less than 10 wt %,preferably less than 5 wt %, or preferably 0 wt %, or, optionally,greater than 0 wt % or greater than 1 wt %), based on the total weightof the alumoxane activator.

The minimum activator metal-to-zirconium (preferably aluminum from thealumoxane to zirconium from the zirconocene catalyst of the catalystsystem) ratio is a 1:1 molar ratio. Alternate preferred ratios includeup to 5000:1, preferably up to 500:1, preferably up to 200:1, preferablyup to 100:1, or preferably from 1:1 to 50:1.

In some embodiments of this invention, the alumoxane activator may besupported on the support material prior to contact with the metallocenecompound. In other embodiments, the alumoxane activator is combined withthe metallocene compound prior to being placed upon the supportmaterial.

Optional Cocatalysts

In addition to these alumoxane activator compounds, cocatalysts may beused. Aluminum alkyl or organoaluminum compounds which may be utilizedas cocatalysts (or scavengers) include, for example, triethylaluminum,tri-isobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, dibutyl zinc, diethyl zinc, and the like.

Preferably, cocatalyst is present at a molar ratio of cocatalyst metalto transition metal of less than 100:1, preferably less than 50:1,preferably less than 15:1, preferably less than 10:1. In alternateembodiments, the cocatalyst is present at 0 wt %.

Other additives may also be used, as desired, such as one or morescavengers, promoters, modifiers, reducing agents, oxidizing agents,aluminum alkyls, or silanes.

Metallocene Compounds

A metallocene catalyst is defined as an organometallic compound with atleast one π-bound cyclopentadienyl moiety (or substitutedcyclopentadienyl moiety) and more frequently two π-boundcyclopentadienyl-moieties or substituted moieties. This includes otherπ-bound moieties such as indenyls or fluorenyls or derivatives thereof.The inventors have surprisingly found that the zirconium analogs ofuseful metallocenes have better activity and produce greater amounts ofvinyl chain ends.

For the purposes of this invention and the claims thereto, when catalystsystems are described as comprising neutral stable forms of thecomponents, it is well understood by one of ordinary skill in the art,that the ionic form of the component is the form that reacts with themonomers to produce polymers.

Useful metallocene compounds of this invention are represented by theformula:

wherein:

T is Si or Ge (preferably T is Si);

each R^(A) is a C₁ to C₂₀ substituted or unsubstituted hydrocarbyl group(preferably R^(A) is methyl or ethyl; preferably methyl);

each R^(B) is, independently, H or a C₁ to C₈ substituted orunsubstituted hydrocarbyl group, or a group represented by the formula—CH₂R^(x) (preferably R^(B) is H, ethyl, n-propyl, n-butyl, benzyl,sec-butyl, or —CH₂-cyclopropyl);

wherein R^(x) is a C₁ to C₂₀ substituted or unsubstituted hydrocarbylgroup, provided that at least one R^(B) is methyl or a group representedby the formula —CH₂R^(x) (preferably —CH₂R^(x) is one of ethyl,n-propyl, n-butyl, sec-butyl, —CH₂-cyclopropyl, or benzyl groups);

each R^(C) is, independently, H or a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl group (preferably R^(C) is H);

each A is independently selected from the group consisting of C₁ to C₂₀substituted or unsubstituted hydrocarbyl groups, hydrides, amides,amines, alkoxides, sulfides, phosphides, halides, dienes, phosphines,and ethers (preferably A is Cl or methyl), and two A groups can form acyclic structure including aromatic, partially saturated, or saturatedcyclic or fused ring system;

each X is, independently, hydrogen, halogen, or a substituted orunsubstituted C₁ to C₂₀ hydrocarbyl, and two X groups can form a cyclicstructure including aromatic, partially saturated, or saturated cyclicor fused ring system (preferably X is methyl, ethyl, silacyclobutyl, orsilacyclopentyl); and

further provided that any of adjacent R^(A), R^(B), and/or R^(C) groupsmay form a fused ring or multicenter fused ring systems, where the ringsmay be substituted or unsubstituted, and may be aromatic, partiallyunsaturated, or unsaturated (preferably R^(B) and/or R^(A) or R^(C) fuseto form a substituted or unsubstituted indene or a fluorene; preferablythe metallocene compound is not a bis-fluorenyl compound).

In preferred embodiments, the metallocene compound is asymmetric, whichis defined to mean that groups of different sizes are bridged by the TX₂bridge, for example, the metallocene compound may be abis-cyclopentadienyl-indenyl compound, a bis cyclopentadienyl-fluorenylcompound, a bis-indenyl-fluorenyl compound. In other embodiments, themetallocene compound is symmetric, for example, a bis-indenyl compound.

Preferred metallocene compounds may be represented by the formula:

wherein R^(B) is as defined above.

Particularly preferred metallocene compounds may be represented by theformula:

Other preferred metallocenes include:

Me₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂; Me₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;Me₂Si(3-n-butylCpMe₃)(C₁₃H₈)ZrCl₂; Me₂Si(3-n-butylCpMe₃)(C₁₃H₈)ZrMe₂;Me₂Si(3-benzylCpMe₃)(C₁₃H₈)ZrCl₂; Me₂Si(3-benzylCpMe₃)(C₁₃H₈)ZrMe₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(C₁₃H₈)ZrCl₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(C₁₃H₈)ZrMe₂;Me₂Ge(3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂; Me₂Ge(3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;Et₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂; Et₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;(Hexyl)₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂;(Hexyl)₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;[(C₃H₆)Si](3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂;[(C₃H₆)Si](3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;[(C₄H₈)Si](3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂;[(C₄H₈)Si](3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂; Me₂Si(CpMe₄)(C₁₃H₈)ZrCl₂;Me₂Si(CpMe₄)(C₁₃H₈)ZrMe₂; Me₂Ge(CpMe₄)(C₁₃H₈)ZrCl₂;Me₂Ge(CpMe₄)(C₁₃H₈)ZrMe₂; Et₂Si(CpMe₄)(C₁₃H₈)ZrCl₂;Et₂Si(CpMe₄)(C₁₃H₈)ZrMe₂; (Hexyl)₂Si(CpMe₄)(C₁₃H₈)ZrCl₂;(Hexyl)₂Si(CpMe₄)(C₁₃H₈)ZrMe₂; [(C₃H₆)Si](CpMe₄)(C₁₃H₈)ZrCl₂;[(C₃H₆)Si](CpMe₄)(C₁₃H₈)ZrMe₂; [(C₄H₈)Si](CpMe₄)(C₁₃H₈)ZrCl₂;[(C₄H₈)Si](CpMe₄)(C₁₃H₈)ZrMe₂; Me₂Si(3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Si(3-n-butylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Si(3-benzylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Ge(3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Et₂Si(3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;(Hexyl)₂Si(3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;[(C₃H₆)Si](3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;[(C₄H₈)Si](3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;[(C₃H₆)Si](CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;[(C₃H₆)Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;[(C₃H₆)Si](CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;[(C₃H₆)Si](CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;[(C₃H₆)Si](CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;[(C₄H₈)Si](CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂; [(C₄H₈)Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;[(C₄H₈)Si](CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;[(C₄H₈)Si](CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;[(C₄H₈)Si](CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Me₂Si(3-n-propylCpMe₃)(CpMe₄)ZrCl₂; Me₂Si(3-n-propylCpMe₃)(CpMe₄)ZrMe₂;Me₂Si(3-n-butylCpMe₃)(CpMe₄)ZrCl₂; Me₂Si(3-n-butylCpMe₃)(CpMe₄)ZrMe₂;Me₂Si(3-benzylCpMe₃)(CpMe₄)ZrCl₂; Me₂Si(3-benzylCpMe₃)(CpMe₄)ZrMe₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(CpMe₄)ZrCl₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(CpMe₄)ZrMe₂;Me₂Ge(3-n-propylCpMe₃)(CpMe₄)ZrCl₂; Me₂Ge(3-n-propylCpMe₃)(CpMe₄)ZrMe₂;Et₂Si(3-n-propylCpMe₃)(CpMe₄)ZrCl₂; Et₂Si(3-n-propylCpMe₃)(CpMe₄)ZrMe₂;(Hexyl)₂Si(3-n-propylCpMe₃)(CpMe₄)ZrCl₂;(Hexyl)₂Si(3-n-propylCpMe₃)(CpMe₄)ZrMe₂;[(C₃H₆)Si](3-n-propylCpMe₃)(CpMe₄)ZrCl₂;[(C₃H₆)Si](3-n-propylCpMe₃)(CpMe₄)ZrMe₂;[(C₄H₈)Si](3-n-propylCpMe₃)(CpMe₄)ZrCl₂;[(C₄H₈)Si](3-n-propylCpMe₃)(CpMe₄)ZrMe₂;rac-Me₂Si(2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-Me₂Si(2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-Me₂Si(2-Me,3-n-butylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-Me₂Si(2-Me,3-n-butylC₉H₄)₂ZrCl₂;rac-Me₂Si(2-Me,3-CH₂-cyclopropylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-Me₂Si(2-Me,3-CH₂-cyclopropylC₉H₄)₂ZrCl₂;rac-Me₂Ge(2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-Me₂Ge(2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-Et₂Si(2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;Et₂Si(2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-(Hexyl)₂Si(2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-(Hexyl)₂Si(2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-[(C₃H₆)Si](2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-[(C₃H₆)Si](2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-[(C₄H₈)Si](2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-[(C₄H₈)Si](2-Me,3-n-propylC₉H₄)₂ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;[(C₃H₆)Si](C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;[(C₃H₆)Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;[(C₃H₆)Si](C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;[(C₃H₆)Si](C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;[(C₃H₆)Si](C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;[(C₄H₈)Si](C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;[(C₄H₈)Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;[(C₄H₈)Si](C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;[(C₄H₈)Si](C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;[(C₄H₈)Si](C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂; and zirconiumdimethyl analogs of the above zirconium dichloride compounds wherein theCl groups on the Zr are replaced with CH₃ groups; wherein Me is methyl;Et is ethyl; C₉H₄ is an indenyl group; C₁₃H₈ is a fluorenyl group;[(C₃H₆)Si] is silacyclobutyl bridge; and [(C₄H₈)Si] is silacyclopentylbridge.

Methods of Making the Catalyst System

Any method of supporting the metallocene compound and alumoxaneactivator may be used. In some embodiments of this invention, thesupport material, typically having reactive surface groups, typicallyhydroxyl groups, is slurried in a non-polar solvent and the resultingslurry is contacted with a solution of an alumoxane activator,preferably TMA-depleted alumoxane. The slurry mixture may be heated toabout 0° C. to about 70° C., preferably to about 25° C. to about 60° C.,preferably at room temperature (25° C.). Contact times typically rangefrom about 0.5 hours to about 24 hours, from about 2 hours to about 16hours, or from about 4 hours to about 8 hours.

Suitable non-polar solvents are materials in which all of the reagentsused herein, i.e., the activator, and the metallocene compound, are atleast partially soluble and which are liquid at reaction temperatures.Preferred non-polar solvents are alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene, and ethylbenzene, alone or in combination, may alsobe employed.

In embodiments of the invention herein, the support material iscontacted with a solution of an alumoxane activator to form a supportedalumoxane activator. The period of time for contact between theactivator and the support material is as long as is necessary to titratethe reactive groups on the support material. To “titrate” is meant toreact with available reactive groups on the surface of the supportmaterial, thereby reducing the surface hydroxyl groups by at least 80%,at least 90%, at least 95%, or at least 98%. The surface reactive groupconcentration may be determined based on the calcining temperature andthe type of support material used. The support material calciningtemperature affects the number of surface reactive groups on the supportmaterial available to react with the metallocene compound and analumoxane activator: the higher the drying temperature, the lower thenumber of sites. For example, where the support material is silicawhich, prior to the use thereof in the first catalyst system synthesisstep, is dehydrated by fluidizing it with nitrogen and heating at about600° C. for about 16 hours, a surface hydroxyl group concentration ofabout 0.5 to about 0.9 millimoles per gram, preferably about 0.7(mmols/gm) is typically achieved. Thus, the exact molar ratio of theactivator to the surface reactive groups on the carrier will vary.Preferably, this is determined on a case-by-case basis to assure thatonly so much of the activator is added to the solution as will bedeposited onto the support material without leaving excess of theactivator in the solution.

The amount of the activator which will be deposited onto the supportmaterial without leaving excess in the solution can be determined in anyconventional manner, e.g., by adding the activator to the slurry of thecarrier in the solvent, while stirring the slurry, until the activatoris detected as a solution in the solvent by any technique known in theart, such as by ¹H NMR. For example, for the silica support materialheated at about 600° C., the amount of the activator added to the slurryis such that the molar ratio of Al to the hydroxyl groups (OH) on thesilica is about 0.5:1 to about 4:1, preferably about 0.8:1 to about 3:1,more preferably about 0.9:1 to about 2:1 and most preferably about 1:1.The amount of Al in/on the silica may be determined by using ICPES(Inductively Coupled Plasma Emission Spectrometry), which is describedin J. W. Olesik, “Inductively Coupled Plasma-Optical EmissionSpectroscopy,” in the Encyclopedia of Materials Characterization, C. R.Brundle, C. A. Evans, Jr. and S. Wilson, eds., Butterworth-Heinemann,Boston, Mass., 1992, pp. 633-644. In another embodiment, it is alsopossible to add such an amount of the activator which is in excess ofthat which will be deposited onto the support material, and then remove,e.g., by filtration and washing.

The supported activator is then slurried into an appropriate solvent,preferably a non-polar solvent. Preferred non-polar solvents arealkanes, such as isopentane, hexane, n-heptane, octane, nonane, anddecane, although a variety of other materials including cycloalkanes,such as cyclohexane, aromatics, such as benzene, toluene, andethylbenzene, may also be employed. The metallocene compound is added tothe slurry mixture and heated to a temperature in the range of from 0°C. to about 70° C., preferably from about 25° C. to about 60° C., mostpreferably at 25° C. Contact times typically range from about 0.5 hoursto about 24 hours, from about 2 hours to about 16 hours, or from about 4hours to about 8 hours. The volatiles are removed to yield the supportedcatalyst system, preferably as a free-flowing solid.

In other embodiments, the metallocene compound is contacted with thealumoxane activator in solution, preferably in a solution of non-polarsolvent, such as those above. The solution may be heated to 0° C. toabout 70° C., preferably to about 25° C. to about 60° C., preferably at25° C. Contact times may range from about 0.5 hours to about 24 hours,from about 2 hours to about 16 hours, or from about 4 hours to about 8hours. The metallocene-activator solution is then contacted with thesupport material to form a slurry mixture. The slurry mixture may beheated to 0° C. to about 70° C., preferably to about 25° to about 60°C., preferably at 25° C. Contact times may range from about 0.5 hours toabout 24 hours, from about 2 hours to about 16 hours, or from about 4hours to about 8 hours. The volatiles are removed, preferably undervacuum, to yield the supported catalyst system, preferably as afree-flowing solid.

In some embodiments, the weight ratio of the zirconocene catalyst to thesolid support material may be from about 10:1 to about 0.0001:1, fromabout 1:1 to about 0.001:1, or from about 0.1:1 to about 0.001:1. Theweight ratio of the support material to the alumoxane activator compoundmay range from about 1:10 to about 100:1, from about 1:1 to about 100:1,or from about 1:1 to about 10:1.

In some embodiments, the supported catalyst system is resuspended in aparaffinic agent, such as mineral oil, for easy addition to a reactorsystem.

Processes to Produce Polyethylene Having Allyl Chain Ends

Accordingly, the present invention relates to a process to producepolyethylene comprising:

(a) contacting ethylene (and preferably less than 2 wt % of a C₃ to C₄₀alphaolefin monomer, alternately from 2 to about 20 wt % of a C₃ to C₄₀alphaolefin monomer, alternately 0 wt % of a C₃ to C₄₀ alphaolefinmonomer) with the supported metallocene catalyst system described above(preferably with less than 1000 ppm hydrogen, preferably less than 100ppm hydrogen, preferably less than 50 ppm hydrogen, preferably less than10 ppm hydrogen, and optionally, preferably 0 wt % of hydrogen)(preferably at a temperature in the range of about 40° C. to about 150°C., preferably from about 50° C. to 120° C., preferably from about 60°C. to 110° C., and/or a pressure in the range of from about 0.55 MPa toabout 2.4 MPa, preferably from about 0.62 MPa to about 2.2 MPa,preferably from about 0.75 MPa to about 2.07 MPa);(b) obtaining a vinyl terminated polyethylene having:

(i) at least 60% allyl chain ends (preferably at least 65%, preferablyat least 70%, preferably at least 75%, preferably at least 80%,preferably at least 85%, preferably at least 90%, preferably at least95%, preferably at least 96%, preferably at least 97%, preferably atleast 98%, preferably at least 99%, or preferably at least 100%), basedon the total unsaturations;

(ii) a molecular weight distribution of less than or equal to 4.0(preferably less than or equal to 3.8, preferably less than or equal to3.5, preferably less than or equal to 3.2, preferably less than or equalto 3.0, preferably less than or equal to 2.8, or preferably less than orequal to 2.5; and preferably greater than 1);

(iii) an Mn (¹HNMR) of at least 20,000 g/mol (preferably at least 25,000g/mol, preferably at least 30,000 g/mol, preferably at least 40,000g/mol, preferably at least 50,000 g/mol, and, optionally, less than125,000 g/mol, preferably less than 120,000 g/mol, 115,000 g/mol,110,000 g/mol, or 100,000 g/mol);

(iv) optionally, an Mn (GPC)/Mn (¹HNMR) in the range of from about 0.8to about 1.2 (preferably from about 0.9 to about 1.1, preferably fromabout 0.95 to about 1.1); and

(v) optionally, a g′(vis) of greater than 0.95 (preferably greater than0.96, preferably greater than 0.98, preferably greater than 0.99, and,optionally, preferably less than or equal to 1.0).

Monomers

In embodiments of this invention, where homopolyethylene is produced,the process comprises contacting ethylene and 0 wt % of monomer,specifically 0 wt % of C₃ to C₄₀ alphaolefin comonomer with a supportedmetallocene catalyst system.

In embodiments where an ethylene copolymer is produced, the processcomprises contacting ethylene monomer with from about 0.1 wt % to about20 wt % of a C₃ to C₄₀ alphaolefin monomer (preferably at least 2 wt %comonomer is used, preferably at least 5 wt %, preferably at least 8 wt%, preferably at least 10 wt %, optionally, preferably less than 20 wt %comonomer is used, preferably less than 15 wt %, preferably less than 12wt %).

Useful comonomers include C₃ to C₄₀ alphaolefin monomers, preferably C₄to C₄₀ alphaolefin monomers, preferably C₅ to C₄₀ alphaolefin monomers,preferably C₅ to C₂₀ alphaolefin monomers, or C₃ to C₁₂ alphaolefinmonomers. Examples of useful comonomers include propylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and1-undecene.

Polymerization Processes

Generally speaking, the polymerization process comprises contacting oneor more olefinically unsaturated monomers with the supported catalystsystem of the invention. The catalysts according to the invention areparticularly suited to use in gas phase or slurry polymerizationprocesses where heterogeneous catalysts are typically used. Theheterogeneous catalysts of the invention are typically supported oninert support particles, which are then used in a gas phase or liquidprocess wherein the monomers are contacted with the supported catalystsystems.

Generally, a fluidized gas bed process is used for producing polymers,with a gaseous stream containing one or more monomers being continuouslycycled through the fluidized bed in the presence of a catalyst underreactive conditions. The gaseous stream is withdrawn from the fluidizedbed and recycled back into the reactor. Simultaneously, polymer productis withdrawn from the reactor and fresh monomer is added to replace thepolymerized monomer. (See, for example, U.S. Pat. Nos. 4,543,399;4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304;5,453,471; 5,462,999; 5,616,661; and 5,668,228.)

In a slurry polymerization, a suspension of solid, particulate polymeris formed in a liquid polymerization diluent medium to which monomer andcomonomers along with catalyst are added. The suspension includingdiluent is intermittently or continuously removed from the reactor wherethe volatile components are separated from the polymer and recycled,optionally, after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedis preferably liquid under the conditions of polymerization andrelatively inert. Preferably, a propane, hexane or an isobutane mediumis employed. Non-limiting examples of slurry processes includecontinuous loop or stirred tank processes. Further examples of slurryprocesses are described in U.S. Pat. No. 4,613,484. In some embodimentsof this invention, the conversion of olefin monomer is at least 10%,based upon polymer yield and the weight of the monomer entering thereaction zone, preferably 20% or more, preferably 30% or more,preferably 50% or more, preferably 80% or more. Conversion is the amountof monomer that is converted to polymer product, is reported as mol %,and is calculated based on the polymer yield and the amount of monomerfed into the reactor.

In some embodiments of this invention, the catalyst productivity is 4500g/mmol/hour or more, preferably 5000 g/mmol/hour or more, preferably10,000 g/mmol/hour or more, preferably 50,000 g/mmol/hour or more. Inother embodiments, the productivity is at least 80,000 g/mmol/hour,preferably at least 150,000 g/mmol/hour, preferably at least 200,000g/mmol/hour, preferably at least 250,000 g/mmol/hour, preferably atleast 300,000 g/mmol/hour. “Catalyst productivity” is a measure of howmany grams of polymer (P) are produced using a polymerization catalystcomprising W g of catalyst (cat), over a period of time of T hours, andmay be expressed by the following formula: P/(T×W) and expressed inunits of gPgcat⁻¹hr⁻¹.

Preferred polymerizations can be run at any temperature and/or pressuresuitable to obtain the desired vinyl terminated polyethylenes. Thepolymerization may be ran at any suitable temperature, such as at atemperature in the range of from about 40° C. to 150° C., preferablyfrom about 60° C. to 120° C.; and at any suitable pressure, preferablepressures may be in the range of from about 0.55 MPa to about 2.4 MPa,preferably from about 0.60 MPa to about 2.2 MPa, or preferably fromabout 0.65 MPa to about 2.0 MPa.

In a typical polymerization, the run time of the reaction may be up to300 minutes, preferably in the range of from about 5 to 250 minutes, orpreferably from about 10 to 120 minutes.

In some embodiments of this invention, vinyl terminated polyethylene maybe advantageously produced in the presence of hydrogen. Preferably,ethylene may be contacted with the metallocene catalyst system in thepresence of less than 1000 ppm hydrogen, preferably less than 100 ppmhydrogen, preferably less than 50 ppm hydrogen, or preferably less than10 ppm hydrogen. In other embodiments of this invention, there is 0 wt %hydrogen present. Preferably, the catalyst productivity (calculated asg/mmol catalyst/hr) is at least 20% higher than the same reactionwithout hydrogen present, preferably at least 50% higher, preferably atleast 100% higher.

In a preferred embodiment of the present invention, the catalyst systemused in the polymerization comprises no more than one catalyst compound.A “reaction zone” also referred to as a “polymerization zone” is avessel where polymerization takes place, for example, a batch reactor.When multiple reactors are used in either series or parallelconfiguration, each reactor is considered as a separate polymerizationzone. For a multi-stage polymerization in both a batch reactor and acontinuous reactor, each polymerization stage is considered as aseparate polymerization zone. In tubular reactors, different parts ofthe tube are considered different zones. In a preferred embodiment, thepolymerization occurs in one reaction zone.

Cocatalysts such as triethylaluminum, tri-isobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, diethyl aluminum chloride,dibutyl zinc, diethyl zinc, and the like may be used. In someembodiments, the process of this invention is conducted in the absenceof or essentially free of any scavengers, such as triethylaluminum,tri-isobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, dibutyl zinc, diethyl zinc, and the like.

Ethylene Polymers

The inventors have surprisingly found that processes of this inventionwith the selected supported catalyst system produce ethylenehomopolymers and copolymers having high percentages of allyl chain endsand a narrow molecular weight distribution.

In embodiments of this invention, the processes of this inventionproduce a vinyl terminated polyethylene (preferably the polyethylene isin the form of free-flowing, discrete particles) having: (a) at least60% allyl chain ends (preferably 65%, 70%, 80%, 90%, 95%, 96%, 97%, 98%,99%, or 100%), based on the total unsaturations; (b) a molecular weightdistribution of less than or equal to 4.0 (preferably less than or equalto 3.8, 3.6, 3.5, 3.4, 3.2, 3.0, 2.8, or 2.5; and preferably greaterthan 1.0); (c) a g′(vis) of greater than 0.95 (preferably greater than0.96, preferably greater than 0.98, greater than 0.98, and, optionally,preferably less than or equal to 1.0); (d) an Mn (¹HNMR) of at least20,000 g/mol (preferably at least 25,000, preferably at least 30,000,preferably at least 40,000, preferably at least 50,000, and, optionally,preferably less than 125,000 g/mol, preferably less than 120,000 g/mol,115,000 g/mol, 110,000 g/mol, or 100,000 g/mol); and, optionally, (e) anMn (GPC)/Mn (¹HNMR) in the range of from about 0.8 to about 1.2(preferably from about 0.85 to about 1.15, preferably from about 0.90 toabout 1.10, and preferably from about 0.95 to about 1.00).

The processes of this invention preferably produce a vinyl terminatedpolyethylene in the form of free-flowing, discrete particles. Preferablythe free-flowing discrete particles of the polymer concentrate of thepresent invention may be regarded as a pourable free-flowing polymerconcentrate. As such, the particles of the present invention are nottacky or sticky, and thus do not block, which is to say the particles donot stick to one another nor to other surfaces so as to formagglomerates comprising a plurality of pellets to an extent whichprevents the pellets from being pourable.

By “pourable free-flowing” it is meant that the particles will flowthrough a funnel and yield a pourability value according to ASTM D1895Method B modified to use a funnel having a 29 mm bottom opening asdescribed herein, preferably both initially and after elevatedtemperature storage (e.g., storage at 120° F. for 7 days). Accordingly,the particles of the present invention are pourable free-flowing in thatthey may be poured through a funnel having a 2.9 cm opening at thenarrow end.

An initial pourability value (i.e., prior to aging or storage) of theparticles of the present invention may be about 120 seconds or less,when determined according to ASTM D1895 Method B modified to use afunnel having a 29 mm bottom opening. Preferably, the pourability valueis about 60 seconds or less, more preferably about 30 seconds or less,still more preferably about 10 seconds or less, more preferably about 5seconds or less, still more preferably about 2 seconds or less, whendetermined according to ASTM D1895 Method B modified to use a funnelhaving a 29 mm bottom opening. Accordingly, the polymer concentrate ofthe present invention may preferably be pelletized into a plurality ofpourable free flowing particles that may be poured through a funnelhaving a 29 mm bottom opening. In a preferred embodiment, the pluralityof pourable free flowing particles of the polymer concentrate may bepoured through a funnel having a 29 mm bottom opening in 120 seconds orless, preferably in 60 seconds or less, more preferably in 30 seconds orless, more preferably in 20 seconds or less.

After aging of the particles at 120° F. for 7 days, the aged pourabilityvalue of the particles of the present invention may be about 300 secondsor less, when determined according to ASTM D1895 Method B modified touse a funnel having a 29 mm bottom opening. Preferably, after aging thepourability value is about 200 seconds or less, more preferably about100 seconds or less, still more preferably about 50 seconds or less,more preferably about 30 seconds or less, still more preferably about 10seconds or less, when determined according to ASTM D1895 Method Bmodified to use a funnel having a 29 mm bottom opening.

In some embodiments, the processes of this invention, such as a slurryprocess, produce an ethylene homopolymer having: an Mn (i) at least 95%allyl chain ends (preferably at least 96%, preferably at least 97%,preferably at least 98%, preferably at least 99%, or preferably 100%),based on the total unsaturations; (ii) a molecular weight distributionof less than or equal to 3.5 (preferably less than 3.2, preferably lessthan 3.0, preferably less than 2.8, preferably less than 2.5); (iii) anMn (¹HNMR) of at least 20,000 g/mol (preferably at least 25,000,preferably at least 30,000, preferably at least 40,000, preferably atleast 50,000, or less than 125,000 g/mol, preferably less than 120,000g/mol, 115,000 g/mol, 110,000 g/mol, or 100,000 g/mol); optionally, (iv)an Mn (GPC)/Mn (¹HNMR) in the range of from about 0.8 to about 1.2(preferably from about 0.9 to about 1.1, preferably from about 0.95 toabout 1.1); and, optionally, (v) a g′(vis) of greater than 0.95(preferably greater than 0.96, preferably greater than 0.98, preferablygreater than 0.99, and, optionally, preferably less than or equal to1.0).

In other embodiments, the processes of this invention produce anethylene copolymer having (i) at least 60% allyl chain ends (preferablyat least 65% allyl chain ends, preferably at least 70% allyl chain ends,preferably at least 75% allyl chain ends, preferably at least 80% allylchain ends), based on the total unsaturations; (ii) a molecular weightdistribution of less than or equal to 4.0 (preferably less than or equalto 3.8, preferably less than or equal to 3.5, preferably less than orequal to 3.2, preferably less than or equal to 3.0, preferably less thanor equal to 2.8, preferably less than or equal to 2.5); (iii) an Mn(¹HNMR) of at least 20,000 g/mol (preferably at least 25,000, preferablyat least 30,000, preferably at least 40,000, preferably at least 50,000,and, optionally, less than 125,000 g/mol, preferably less than 120,000g/mol, 115,000 g/mol, 110,000 g/mol, or 100,000 g/mol); optionally, (iv)an Mn (GPC)/Mn (¹HNMR) in the range of from about 0.8 to about 1.2(preferably from about 0.9 to about 1.1, preferably from about 0.95 toabout 1.1); and, optionally, (v) a g′(vis) of greater than 0.95(preferably greater than 0.96, preferably greater than 0.98, preferablygreater than 0.99, and, optionally, preferably less than or equal to1.0).

In particular embodiments, the copolymer may be an ethylene/propylene,ethylene/butene, ethylene/pentene, ethylene/hexene, or ethylene/octenecopolymer.

Ethylene homopolymers of this invention have at least 95% allyl chainends (preferably at least 96%, preferably at least 97%, preferably atleast 98%, preferably at least 99%, or preferably 100%), based on thetotal unsaturations. Ethylene copolymers of this invention have at least60% allyl chain ends (preferably at least 65%, preferably at least 70%,preferably at least 75%, preferably at least 80%, preferably at least85%, preferably at least 90%, preferably at least 95%, preferably atleast 96%, preferably at least 97%, preferably at least 98%, preferablyat least 99%, or preferably 100%), based on the total unsaturations. Thenumber of allyl chain ends is determined using ¹H NMR at 120° C. usingdeuterated tetrachloroethane as the solvent on an at least 250 MHz NMRspectrometer. Resconi has reported proton assignments (neatperdeuterated tetrachloroethane used for proton spectra; all spectrawere recorded at 100° C. on a Bruker spectrometer operating at 500 MHzfor proton) for vinyl terminated oligomers in J. American Chemical Soc.,114, 1992, 1025-1032. Allyl chain ends are reported as a molarpercentage of the total number of moles of unsaturated groups (that is,the sum of allyl chain ends, vinylidene chain ends, and vinylene chainends).

Polymers produced by processes of this invention have an Mn (¹HNMR) ofat least 20,000 g/mol (preferably at least 25,000, preferably at least30,000, preferably at least 40,000, preferably at least 50,000, and,optionally, less than 125,000 g/mol, preferably less than 120,000 g/mol,115,000 g/mol, 110,000 g/mol, or 100,000 g/mol). ¹H NMR data iscollected at 380K in a 5 mm probe in C₂D₂Cl₄ or toluene-d8 using aVarian or a Bruker spectrometer with a ¹H frequency of at least 400 MHz(available from Agilent Technologies, Santa Clara, Calif.). For thepurpose of the claims, ¹H NMR data is collected at 380K in a 5 mm probein toluene-d8 using a Bruker spectrometer.

¹H NMR data was recorded using a maximum pulse width of 45° C., 8seconds between pulses and signal averaging 120 transients. Spectralsignals were integrated and the number of unsaturation types per 1000carbons was calculated by multiplying the different groups by 1000 anddividing the result by the total number of carbons. Mn (¹H NMR) wascalculated by dividing the total number of unsaturated species into14,000, and has units of g/mol.

The chemical shift regions for the olefin types are defined to bebetween the following spectral regions.

Unsaturation Type Region (ppm) Number of hydrogens per structure Vinyl4.95-5.10 2 Vinylidene (VYD) 4.70-4.84 2 Vinylene 5.31-5.55 2Trisubstituted 5.11-5.30 1

Polymer produced by processes of this invention also have a Mn (GPC)/Mn(¹HNMR) in the range of from about 0.8 to about 1.2 (preferably fromabout 0.9 to about 1.1, preferably from about 0.95 to about 1.1).

Mn (GPC), Mw, Mz and g′(vis) were determined using a Gel PermeationChromatography (GPC) method using a High Temperature Size ExclusionChromatograph (SEC, either from Waters Corporation, Milford, Mass. orPolymer Laboratories (now part of Varian Inc., available from AgilentTechnologies)), equipped with a differential refractive index detector(DRI). Experimental details are described in: T. Sun, P. Brant, R. R.Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19,6812-6820, (2001) and references therein. Three Polymer LaboratoriesPLgel 10 mm Mixed-B columns are used. The nominal flow rate was 0.5cm³/min and the nominal injection volume is 300 μL. The various transferlines, columns, and differential refractometer (the DRI detector) werecontained in an oven maintained at 135° C. Solvent for the SECexperiment was prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.7μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. TheTCB was then degassed with an online degasser before entering the SEC.Polymer solutions were prepared by placing dry polymer in a glasscontainer, adding the desired amount of TCB, then heating the mixture at160° C. with continuous agitation for about 2 hours. All quantities weremeasured gravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units were 1.463 g/mL at room temperatureand 1.324 g/mL at 135° C. The injection concentration was from 1.0 to2.0 mg/mL, with lower concentrations being used for higher molecularweight samples. Prior to running each sample the DRI detector and theinjector were purged. Flow rate in the apparatus was then increased to0.5 mL/minute and the DRI was allowed to stabilize for 8 to 9 hoursbefore injecting the first sample. The concentration, c, at each pointin the chromatogram was calculated from the baseline-subtracted DRIsignal, I_(DRI), using the following equation:

c=K _(DRI) I _(DRI)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 135° C. and λ=690 nm. For purposes of thisinvention and the claims thereto (dn/dc)=0.104 for propylene polymersand ethylene polymers and 0.1 otherwise. Units of parameters usedthroughout this description of the SEC method were: concentration wasexpressed in g/cm³, molecular weight was expressed in g/mol, andintrinsic viscosity was expressed in dL/g.

Polymers produced by the processes of this invention also have a g′(vis)of greater than 0.95 (preferably greater than 0.96, preferably greaterthan 0.98, preferably greater than 0.99, and, optionally, preferablyless than or equal to 1.0). The branching index (g′(vis)) is calculatedusing the output of the SEC-DRI-LS-VIS method as follows. The averageintrinsic viscosity, [η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$

where the summations are over the chromatographic slices, i, between theintegration limits, wherein [η]_(i) is the intrinsic viscosity over thechromatographic slices, i.The branching index g′(vis) is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{k\; M_{v}^{\alpha}}$

where, for purpose of this invention and claims thereto, α=0.695 andk=0.000579 for linear ethylene polymers, α=0.705 k=0.000262 for linearpropylene polymers, and α=0.695 and k=0.000181 for linear butenepolymers. M_(v) is the viscosity-average molecular weight based onmolecular weights determined by LS analysis. See Macromolecules, 2001,34, pp. 6812-6820 and Macromolecules, 2005, 38, pp. 7181-7183, forguidance on selecting a linear standard having similar molecular weightand comonomer content, and determining k coefficients and α exponents.

In any embodiment of the invention, the vinyl terminated polyethylenesdescribed herein may have a melting point (DSC first melt, as describedbelow) of from 60° C. to 130° C., alternately 50° C. to 100° C. Meltingtemperature (T_(m)) and glass transition temperature (Tg) are measuredusing Differential Scanning calorimetry (DSC) using commerciallyavailable equipment such as a TA Instruments 2920 DSC. Typically, 6 to10 mg of the sample, that has been stored at room temperature for atleast 48 hours, is sealed in an aluminum pan and loaded into theinstrument at room temperature. The sample is equilibrated at 25° C.,then it is cooled at a cooling rate of 10° C./min to −80° C., to obtainheat of crystallization (Tc). The sample is held at −80° C. for 5 minand then heated at a heating rate of 10° C./min to 25° C. The glasstransition temperature (Tg) is measured from the heating cycle.Otherwise, the sample is equilibrated at 25° C., then heated at aheating rate of 10° C./min to 150° C. The endothermic meltingtransition, if present, is analyzed for onset of transition and peaktemperature. The melting temperatures reported (Tm) are the peak meltingtemperatures from the first heat unless otherwise specified. For samplesdisplaying multiple peaks, the melting point (or melting temperature) isdefined to be the peak melting temperature (i.e., associated with thelargest endothermic calorimetric response in that range of temperatures)from the DSC melting trace.

In any embodiment of the invention, the vinyl terminated polyethylenesmay have less than 3 wt % of functional groups selected from hydroxide,aryls and substituted aryls, halogens, alkoxys, carboxylates, esters,acrylates, oxygen, nitrogen, and carboxyl; preferably less than 2 wt %,more preferably less than 1 wt %, more preferably less than 0.5 wt %,more preferably less than 0.1 wt %, more preferably 0 wt %, based uponthe weight of the oligomer.

Uses of Ethylene Polymers Having Allyl Chain Ends

The ethylene polymers having high percentages of allyl chain endsprepared herein may be functionalized by reacting a heteroatomcontaining group with the allyl group of the polymer, with or without acatalyst. The reaction product is a functionalized polyethylene, havinga modified group (derived from the heteroatom containing group).Examples include catalytic hydrosilylation, hydroformylation,hydroboration, epoxidation, hydration, dihydroxylation,hydrohalogenation, hydroamination, or maleation with or withoutactivators such as free radical generators (e.g., peroxides).

This invention also relates to: a functionalized polyethylene having:(i) at least 50% modified groups (preferably 60%, 70%, 80%, 90%, 95%,96%, 97%, 98%, 99%, or 100%), based on the sum of the totalunsaturations and modified groups; (ii) a molecular weight distributionof less than or equal to 4.0 (preferably less than or equal to 3.8, 3.6,3.5, 3.4, 3.2, 3.0, 2.8, or 2.5; and preferably greater than 1.0); (iii)a g′(vis) of greater than 0.95 (preferably greater than 0.96, 0.97,0.98, 0.99 or less than or equal to 1.0). Preferably, the functionalizedpolyethylene also has an Mn (GPC) of at least 16,000 g/mol (preferablyat least 25,000, preferably at least 30,000, preferably at least 40,000,preferably at least 50,000, and, optionally, less than 150,000 g/mol,preferably less than 120,000 g/mol, 115,000 g/mol, 110,000 g/mol, or100,000 g/mol). Preferably, the modified group is one or more of anamine, an aldehyde, an alcohol, an acid, a halide, a succinic acid, amaleic acid, and a maleic anhydride. Preferably, the modified group isone or more of an amine, an aldehyde, an alcohol, an acid, a halide, asuccinic acid, a maleic acid, and a maleic anhydride.

In some embodiments, the ethylene polymers having high percentages ofallyl chain ends produced herein are functionalized as described in U.S.Pat. No. 6,022,929; A. Toyota, T. Tsutsui, and N. Kashiwa, PolymerBulletin 48, pp. 213-219, 2002; J. Am. Chem. Soc., 1990, 112, pp.7433-7434; and U.S. Ser. No. 12/487,739, filed on Jun. 19, 2009.

The functionalized polymers can be used in blown films, nanocomposites,pigment compositions, in situ compatibilizers (for use, for example, intie layers), oil additivation, and many other applications. Preferreduses include additives for lubricants and/or fuels.

In particular embodiments of the invention herein, the ethylene polymershaving high percentages of allyl chain ends disclosed herein, orfunctionalized analogs thereof, are useful as additives. In someembodiments, the ethylene polymers having high percentages of allylchain ends disclosed herein, or functionalized analogs thereof, areuseful as additives in a lubricant. Particular embodiments relate to alubricant comprising the ethylene polymers having high percentages ofallyl chain ends disclosed herein, or functionalized analogs thereof.

In other embodiments, the ethylene polymers having high percentages ofallyl chain ends disclosed herein may be used as monomers for thepreparation of polymer products. Processes that may be used for thepreparation of these polymer products include coordinativepolymerization and acid-catalyzed polymerization.

In other embodiments, the invention relates to:

1. A supported catalyst system comprising:(i) a support material (preferably Al₂O₃, ZrO₂, SiO₂, and combinationsthereof, more preferably SiO₂, Al₂O₃, or SiO₂/Al₂O₃);(ii) an alumoxane activator (preferably an alkylalumoxane, preferablymethylalumoxane or isobutylalumoxane) having from about 1 wt % to about14 wt % trimethylaluminum (preferably less than 13 wt %, preferably lessthan 12 wt %, preferably less than 10 wt %, preferably less than 5 wt %,or 0 wt %, or, optionally, greater than 0 wt %, or greater than 1 wt %),based on the weight of the alumoxane activator; and(iii) a metallocene compound represented by the formula:

wherein

T is Si or Ge (preferably T is Si);

each R^(A) is a C₁ to C₂₀ substituted or unsubstituted hydrocarbyl group(preferably R^(A) is methyl or ethyl; preferably methyl);

each R^(B) is, independently, H or a C₁ to C₈ substituted orunsubstituted hydrocarbyl group, or a group represented by the formula—CH₂R^(x) (preferably R^(B) is methyl, n-propyl, n-butyl, benzyl,sec-butyl, or —CH₂-cyclopropyl);

wherein R^(x) is a C₁ to C₂₀ substituted or unsubstituted hydrocarbylgroup, provided that at least one R^(B) is methyl or a group representedby the formula —CH₂R^(x) (preferably —CH₂R^(x) is one of n-propyl,n-butyl, sec-butyl, —CH₂-cyclopropyl or benzyl groups);

each R^(C) is, independently, H or a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl group (preferably R^(C) is H);

each A is independently selected from the group consisting of C₁ to C₂₀substituted or unsubstituted hydrocarbyl groups, hydrides, amides,amines, alkoxides, sulfides, phosphides, halides, dienes, phosphines,and ethers (preferably A is Cl or methyl), and two A groups can form acyclic structure including aromatic, partially saturated, or saturatedcyclic or fused ring system;

each X is, independently, hydrogen, halogen or a substituted orunsubstituted C₁ to C₂₀ hydrocarbyl, and two X groups can form a cyclicstructure including aromatic, partially saturated, or saturated cyclicor fused ring system (preferably X is methyl, ethyl, hexyl,silacyclobutyl, or silacyclopentyl);

further provided that any of adjacent R^(A), R^(B), and/or R^(C) groupsmay form a fused ring or multicenter fused ring systems, where the ringsmay be substituted or unsubstituted, and may be aromatic, partiallyunsaturated, or unsaturated (preferably R^(B) and/or R^(A), or R^(C)fuse to form a substituted or unsubstituted indene or a fluorene;preferably the metallocene compound is not a bis-fluorenyl compound);and

(iv) optionally, at least one cocatalyst or scavenger (preferably one ormore of triethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diethyl aluminum chloride, dibutyl zinc, diethylzinc, and the like).2. The catalyst system of paragraph 1, wherein the metallocene compoundis represented by the following structure, wherein R^(B) is as definedin paragraph 1:

(preferably the metallocene compound is one or more of:Me₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂; Me₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;Me₂Si(3-n-butylCpMe₃)(C₁₃H₈)ZrCl₂; Me₂Si(3-n-butylCpMe₃)(C₁₃H₈)ZrMe₂;Me₂Si(3-benzylCpMe₃)(C₁₃H₈)ZrCl₂; Me₂Si(3-benzylCpMe₃)(C₁₃H₈)ZrMe₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(C₁₃H₈)ZrCl₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(C₁₃H₈)ZrMe₂;Me₂Ge(3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂; Me₂Ge(3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;Et₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂; Et₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;(Hexyl)₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂;(Hexyl)₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;[(C₃H₆)Si](3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂;[(C₃H₆)Si](3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;[(C₄H₈)Si](3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂;[(C₄H₈)Si](3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂; Me₂Si(CpMe₄)(C₁₃H₈)ZrCl₂;Me₂Si(CpMe₄)(C₁₃H₈)ZrMe₂; Me₂Ge(CpMe₄)(C₁₃H₈)ZrCl₂;Me₂Ge(CpMe₄)(C₁₃H₈)ZrMe₂; Et₂Si(CpMe₄)(C₁₃H₈)ZrCl₂;Et₂Si(CpMe₄)(C₁₃H₈)ZrMe₂; (Hexyl)₂Si(CpMe₄)(C₁₃H₈)ZrCl₂;(Hexyl)₂Si(CpMe₄)(C₁₃H₈)ZrMe₂; [(C₃H₆)Si](CpMe₄)(C₁₃H₈)ZrCl₂;[(C₃H₆)Si](CpMe₄)(C₁₃H₈)ZrMe₂; [(C₄H₈)Si](CpMe₄)(C₁₃H₈)ZrCl₂;[(C₄H₈)Si](CpMe₄)(C₁₃H₈)ZrMe₂; Me₂Si(3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Si(3-n-butylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Si(3-benzylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Ge(3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Et₂Si(3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;(Hexyl)₂Si(3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;[(C₃H₆)Si](3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;[(C₄H₈)Si](3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;[(C₃H₆)Si](CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;[(C₃H₆)Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;[(C₃H₆)Si](CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;[(C₃H₆)Si](CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;[(C₃H₆)Si](CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;[(C₄H₈)Si](CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;[(C₄H₈)Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;[(C₄H₈)Si](CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;[(C₄H₈)Si](CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;[(C₄H₈)Si](CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Me₂Si(3-n-propylCpMe₃)(CpMe₄)ZrCl₂; Me₂Si(3-n-propylCpMe₃)(CpMe₄)ZrMe₂;Me₂Si(3-n-butylCpMe₃)(CpMe₄)ZrCl₂; Me₂Si(3-n-butylCpMe₃)(CpMe₄)ZrMe₂;Me₂Si(3-benzylCpMe₃)(CpMe₄)ZrCl₂; Me₂Si(3-benzylCpMe₃)(CpMe₄)ZrMe₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(CpMe₄)ZrCl₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(CpMe₄)ZrMe₂;Me₂Ge(3-n-propylCpMe₃)(CpMe₄)ZrCl₂; Me₂Ge(3-n-propylCpMe₃)(CpMe₄)ZrMe₂;Et₂Si(3-n-propylCpMe₃)(CpMe₄)ZrCl₂; Et₂Si(3-n-propylCpMe₃)(CpMe₄)ZrMe₂;(Hexyl)₂Si(3-n-propylCpMe₃)(CpMe₄)ZrCl₂;(Hexyl)₂Si(3-n-propylCpMe₃)(CpMe₄)ZrMe₂;[(C₃H₆)Si](3-n-propylCpMe₃)(CpMe₄)ZrCl₂;[(C₃H₆)Si](3-n-propylCpMe₃)(CpMe₄)ZrMe₂;[(C₄H₈)Si](3-n-propylCpMe₃)(CpMe₄)ZrCl₂;[(C₄H₈)Si](3-n-propylCpMe₃)(CpMe₄)ZrMe₂;rac-Me₂Si(2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-Me₂Si(2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-Me₂Si(2-Me,3-n-butylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-Me₂Si(2-Me,3-n-butylC₉H₄)₂ZrCl₂;rac-Me₂Si(2-Me,3-CH₂-cyclopropylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-Me₂Si(2-Me,3-CH₂-cyclopropylC₉H₄)₂ZrCl₂;rac-Me₂Ge(2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-Me₂Ge(2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-Et₂Si(2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;Et₂Si(2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-(Hexyl)₂Si(2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-(Hexyl)₂Si(2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-[(C₃H₆)Si](2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-[(C₃H₆)Si](2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-[(C₄H₈)Si](2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-[(C₄—H₈)Si](2-Me,3-n-propylC₉H₄)₂ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;[(C₃H₆)Si](C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;[(C₃H₆)Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;[(C₃H₆)Si](C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;[(C₃H₆)Si](C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;[(C₃H₆)Si](C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;[(C₄H₈)Si](C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;[(C₄H₈)Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;[(C₄H₈)Si](C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;[(C₄H₈)Si](C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;[(C₄H₈)Si](C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂; wherein Me ismethyl, Et is ethyl, C₉H₄ is an indenyl group; C₁₃H₈ is a fluorenylgroup, [(C₃H₆)Si] is silacyclobutyl bridge, and [(C₄H₈)Si] issilacyclopentyl bridge); and further comprising the zirconium dimethylanalogs of the above metallocene compounds, wherein the Cl groups on theZr are preplaced with CH₃ groups.3. A process to produce polyethylene comprising:(a) contacting ethylene with the supported metallocene catalyst systemof paragraphs 1 to 2 (preferably with less than 1000 ppm hydrogen,preferably with less than 100 ppm hydrogen, preferably with less than 50ppm hydrogen, preferably with less than 10 ppm hydrogen, and,optionally, there is 0 wt % hydrogen; preferably, the contacting occursat a temperature in the range of from about 40° C. to about 150° C.;preferably the contacting occurs at a pressure in the range of fromabout 0.55 MPa to about 2.4 MPa);(b) obtaining a vinyl terminated polyethylene (preferably thepolyethylene is in the form of free-flowing, discrete particles) having:(a) at least 60% allyl chain ends (preferably 65%, 70%, 80%, 90%, 95%,96%, 97%, 98%, 99%, or 100%), based on total unsaturations; (b) amolecular weight distribution of less than or equal to 4.0 (preferablyless than or equal to 3.8, 3.6, 3.5, 3.4, 3.2, 3.0, 2.8, or 2.5; andpreferably greater than 1.0); (c) a g′(vis) of greater than 0.95(preferably greater than 0.96, preferably greater than 0.98, preferablygreater than 0.99, and, optionally, preferably less than or equal to1.0); (d) an Mn (¹HNMR) of at least 20,000 g/mol (preferably at least25,000, preferably at least 30,000, preferably at least 40,000,preferably at least 50,000, and, optionally, less than 125,000 g/mol,preferably less than 120,000 g/mol, 115,000 g/mol, 110,000 g/mol, or100,000 g/mol); and, optionally, (e) an Mn (GPC)/Mn (¹HNMR) in the rangeof from about 0.8 to about 1.2 (preferably from about 0.85 to about1.15, preferably from about 0.90 to about 1.10, and preferably fromabout 0.95 to about 1.00).4. The process of paragraph 3, wherein the vinyl terminated polyethyleneis an ethylene polymer having less than 2 wt % (preferably less than 1.5wt %, preferably less than 1.0 wt %, preferably less than 0.5 wt %, or,optionally, 0 wt %); or, alternately, from about 2 wt % to about 20 wt %(preferably from about 2 wt % to about 15 wt %, preferably from about 5wt % to about 15 wt %, preferably from about 5 wt % to about 10 wt %) ofa C₃ to C₄₀ alphaolefin comonomer.5. The process of paragraphs 3 and 4, where the vinyl terminatedpolyethylene is an ethylene homopolymer having 0 wt % of a C₃ to C₄₀alphaolefin comonomer and has greater than 85% allyl chain ends, basedon total unsaturations.6. The process of paragraphs 3 to 5, wherein there is from about 2 wt %to about 20 wt % of a C₃ to C₄₀ alphaolefin comonomer, and the vinylterminated polyethylene has at least 60% allyl chain ends, based ontotal unsaturations.7. A vinyl terminated polyethylene produced by the process of paragraphs3 to 6, (preferably the polyethylene is in the form of free-flowing,discrete particles) having: (i) at least 60% allyl chain ends(preferably 65%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, or 100%), basedon total unsaturations; (ii) a molecular weight distribution of lessthan or equal to 4.0 (preferably less than or equal to 3.8, 3.6, 3.5,3.4, 3.2, 3.0, 2.8, or 2.5; and preferably greater than 1.0); (iii) ag′(vis) of greater than 0.95 (preferably greater than 0.96, preferablygreater than 0.98, preferably greater than 0.99, and, optionally,preferably less than or equal to 1.0); (iv) an Mn (¹HNMR) of at least20,000 g/mol (preferably at least 25,000, preferably at least 30,000,preferably at least 40,000, preferably at least 50,000, and, optionally,less than 125,000 g/mol, preferably less than 120,000 g/mol, 115,000g/mol, 110,000 g/mol, or 100,000 g/mol); and (v) optionally, an Mn(GPC)/Mn (¹HNMR) in the range of from about 0.8 to about 1.2 (preferablyabout from 0.85 to about 1.15, preferably from about 0.90 to about 1.10,and preferably from about 0.95 to about 1.00).8. A reaction product of the vinyl terminated polyethylene of paragraph7 with a modifying agent (preferably the modifying agent reacts with theallyl chain ends of the vinyl terminated polyethylene), wherein thereaction product is a functionalized polyethylene (preferably thefunctionalized polyethylene is in the form of free-flowing, discreteparticles) having: (i) at least 50% modified groups (preferably, themodified group is one of an amine, an aldehyde, an alcohol, a halide, anacid, a succinic acid, a maleic acid, and a maleic anhydride)(preferably 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, or 100%), basedon the sum of the total unsaturations and modified groups; (ii) amolecular weight distribution of less than or equal to 4.0 (preferablyless than or equal to 3.8, 3.6, 3.5, 3.4, 3.2, 3.0, 2.8, or 2.5; andpreferably greater than 1.0); (iii) a g′(vis) of greater than 0.95(preferably greater than 0.96, preferably greater than 0.98, preferablygreater than 0.99, and, optionally, preferably less than or equal to1.0); and (iv) optionally an Mn (GPC) of at least 16,000 g/mol(preferably at least 25,000, preferably at least 30,000, preferably atleast 40,000, preferably at least 50,000, and, optionally, less than150,000 g/mol, preferably less than 120,000 g/mol, 115,000 g/mol,110,000 g/mol, or 100,000 g/mol).9. A composition comprising the vinyl terminated polyethylene and/or thefunctionalized polyethylene of paragraphs 7 and 8 (preferably thecomposition is a nanocomposite, a pigment composition, a compatibilizerfor films, a fuel additive, or a lubricant additive).10. An article comprising the composition of paragraph 9.11. A fuel or a lubricant comprising the reaction product of paragraph8.12. A pigment comprising the reaction product of paragraph 8.

EXAMPLES

The following abbreviations are used below: Me is methyl, Pr isn-propyl, Ph is phenyl, Flu is fluorenyl, Ind is indenyl, Bu is n-butyl,and Bz is benzyl. TMA is trimethylaluminum.

MAO is methylalumoxane and TIBAL is triisobutylaluminum. MAO is obtainedfrom Albemarle (Baton Rouge, La.) and TIBAL is obtained from SigmaAldrich Co. (St. Louis, Mo.), and both were used as received, unlessotherwise stated.

All reactions were carried out under inert atmosphere, preferablynitrogen, unless otherwise stated. All solvents were obtained from SigmaAldrich Co. and dried before use over 3 A molecular sieves (alsoobtained from Sigma Aldrich), unless otherwise stated.

Products were characterized by ¹H NMR and GPC-DRI as follows:

¹H NMR

¹H NMR data was collected at 380K in a 5 mm probe using a Brukerspectrometer with a ¹H frequency of at least 400 MHz (available fromAgilent Technologies, Santa Clara, Calif.). Data was recorded using amaximum pulse width of 45° C., 8 seconds between pulses and signalaveraging 120 transients. Spectral signals were integrated and thenumber of unsaturation types per 1000 carbons was calculated bymultiplying the different groups by 1000 and dividing the result by thetotal number of carbons. Mn was calculated by dividing the total numberof unsaturated species into 14,000, and has units of g/mol.

The chemical shift regions for the olefin types are defined to bebetween the following spectral regions.

Unsaturation Type Region (ppm) Number of hydrogens per structure Vinyl4.95-5.10 2 Vinylidene (VYD) 4.70-4.84 2 Vinylene 5.31-5.55 2Trisubstituted 5.11-5.30 1

GPC-DRI

Mn, Mw, Mz, and g′(vis) were determined using a Gel PermeationChromatography (GPC) method using a High Temperature Size ExclusionChromatograph (SEC, either from Waters Corporation, Milford, Mass. orPolymer Laboratories (now part of Varian Inc., available from AgilentTechnologies)), equipped with a differential refractive index detector(DRI). Experimental details are described in: T. Sun, P. Brant, R. R.Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19,6812-6820, (2001) and references therein. Three Polymer LaboratoriesPLgel 10 mm Mixed-B columns are used. The nominal flow rate was 0.5cm³/min, and the nominal injection volume is 300 μL. The varioustransfer lines, columns and differential refractometer (the DRIdetector) were contained in an oven maintained at 135° C. Solvent forthe SEC experiment was prepared by dissolving 6 grams of butylatedhydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade1, 2, 4 trichlorobenzene (TCB). The TCB mixture was then filteredthrough a 0.7 μm glass pre-filter and subsequently through a 0.1 μmTeflon filter. The TCB was then degassed with an online degasser beforeentering the SEC. Polymer solutions were prepared by placing dry polymerin a glass container, adding the desired amount of TCB, then heating themixture at 160° C. with continuous agitation for about 2 hours. Allquantities were measured gravimetrically. The TCB densities used toexpress the polymer concentration in mass/volume units were 1.463 g/mLat room temperature and 1.324 g/mL at 135° C. The injectionconcentration was from 1.0 to 2.0 mg/mL, with lower concentrations beingused for higher molecular weight samples. Prior to running each samplethe DRI detector and the injector were purged. Flow rate in theapparatus was then increased to 0.5 mL/minute, and the DRI was allowedto stabilize for 8 to 9 hours before injecting the first sample. Theconcentration, c, at each point in the chromatogram was calculated fromthe baseline-subtracted DRI signal, I_(DRI), using the followingequation:

c=K _(DRI) I _(DRI)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 135° C. and λ=690 nm. For purposes of thisinvention and the claims thereto (dn/dc)=0.104 for propylene polymersand ethylene polymers and 0.1 otherwise. Units of parameters usedthroughout this description of the SEC method were: concentration wasexpressed in g/cm³, molecular weight was expressed in g/mol, andintrinsic viscosity was expressed in dL/g.

The branching index (g′(vis)) was calculated using the output of theSEC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

where the summations are over the chromatographic slices, i, between theintegration limits, and wherein [η]_(i) is the intrinsic viscosity overthe chromatographic slices, i.

The branching index g′(vis) was defined as:

where, for purpose of this invention and claims thereto, α=0.695 andk=0.000579 for linear ethylene polymers, α=0.705 k=0.000262 for linearpropylene polymers, and α=0.695 and k=0.000181 for linear butenepolymers. M_(v) is the viscosity-average molecular weight based onmolecular weights determined by LS analysis. See Macromolecules, 2001,34, pp. 6812-6820 and Macromolecules, 2005, 38, pp. 7181-7183, forguidance on selecting a linear standard having similar molecular weightand comonomer content, and determining k coefficients and α exponents.

Example 1

Metallocene compound A, represented by the following structure was usedherein:

Supported MAO (SMAO) with 12% TMA

Methylalumoxane (MAO, 58.5 g, 30 wt % in toluene) was diluted with 80 mLtoluene and Ph₃COH (5.2 g, where Ph is phenyl) was slowly added over a 5minute period. The reaction was stirred for 30 minutes and filteredthrough a medium glass frit. A 0.2 mL aliquot was pulled from thefiltrate to analyze for % TMA by ¹H NMR. The free TMA was analyzed to be11.6 wt % by ¹H NMR.

The solid by-product was further rinsed with toluene (80 ml) and thefiltrate was combined with the original filtrate to provide a filtratemixture. Davison 948 silica gel (49.7 g, calcined at 600° C.) was addedto the filtrate mixture and the reaction mixture was stirred for 3hours. The supported MAO (SMAO) was retained on a glass frit, washedwith pentane (80 mL) and dried in vacuo to yield a free-flowing solid.

Supported A (SMCN A)

SMAO (5.05 g, 11.6% TMA) from above was slurried in hexane (30 mL) andreacted with Metallocene compound A (108 mg) for 2 hours. The volatileswere removed by an N₂ stream and the solid product was dried in vacuo at25° C. for 2 hours to yield a supported Metallocene compound A catalystsystem as an orange free-flowing solid (SMCN A). Elemental Analysis(Galbraith Laboratories): 6.26% Al, 35.9% Si, and 0.40% Zr.

Polymerization Conditions

Polymerization grade ethylene was used and further purified by passingit through a series of columns: 2250 cc Oxyclear cylinder from Labelear(Oakland, Calif.), followed by a 2250 cc column packed with dried 3 Åmole sieves purchased from Aldrich Chemical Company (St. Louis, Mich.),two 500 cc columns packed with dried 5 Å mole sieves purchased fromAldrich Chemical Company, one 500 cc column packed with ALCOA SelexsorbCD (7×14 mesh) purchased from Coastal Chemical Company (Abbeville, La.),and one 500 cc column packed with ALCOA Selexsorb COS (7×14 mesh)purchased from Coastal Chemical Company.

Polymerization grade hexanes were further purified by passing it througha series of columns: two 500 cc Oxyclear cylinders from Labelearfollowed by two 500 cc columns packed with dried 3 Å mole sievespurchased from Aldrich Chemical Company and two 500 cc columns packedwith dried 5 Å mole sieves purchased from Aldrich Chemical Company andused.

Hexene was obtained from Sigma Aldrich (St. Louis, Mo.) and was driedover NaK amalgam.

Reactor Description and Preparation

Polymerizations were conducted in an inert atmosphere (N₂) drybox using48 Cell Parallel Pressure Reactors (PPR) equipped with external heatersfor temperature control, glass inserts (internal volume of reactor=22.5mL), septum inlets, regulated supply of nitrogen, ethylene, and equippedwith disposable PEEK (PolyEtherEtherKetone) mechanical stirrers (800RPM). The PPRs were prepared for polymerization by purging with drynitrogen at 150° C. for 5 hours and then at 25° C. for 5 hours.

Run time was varied, as indicated in Table 1A; Metallocene compound(SMCN A)=0.45 mg. Constant ethylene feed pressure was 220 psi.

TABLE 1A POLYMERIZATION CONDITIONS Hexene Reactor Pressure TemperatureRun Time Yield Run (mg) psi (MPa) (° C.) (s) (mg) 1 0 296.86 (2.05)  702100 65.4 2 0 304.18 (2.10)  85 2101 59.1 3 0 291.67 (2.01)  105 100378.8 4 97.5 296.9 (2.05) 70 2101 72.3 5 97.5 301.9 (2.08) 85.1 1333 80.56 97.5 293.5 (2.02) 105 646 89.3 7 195 295.6 (2.04) 69.9 987 75.6 8 195308.6 (2.13) 85 364 90.5 9 195 294.1 (2.03) 105 1321 85.4 10 325 296.6(2.04) 69.9 260.3 83.9 11 325 305.1 (2.10) 85.1 213.3 105.8 12 325 289.7(1.99) 105 2100 81.1

TABLE 1B POLYETHYLENE CHARACTERIZATION Mn Mn Mw Mw/Mn % % Hexene (¹HNMR) ×10³ (GPC⁺) ×10³ (GPC⁺) ×10³ (GPC/ g′(vis) Run Vinyls VYD* (mol %)g/mol g/mol g/mol GPC)⁺ (GPC⁺) 1 100  0 0   80.9 76.7 207 2.7 1.04  2 —— — — 61.3 162.3 2.6 1.03  3 — — — — 70.9 192.7 2.7 — 4 — — — — 68.4187.6 2.7 1.01  5 — — 0.7 — 58.7 148 2.5 — 6 — — — — 73.2 184.5 2.5 — 7 82 18 1.3 74.9 62.3 169.5 2.7 0.963 8 — — — — 78.6 203 2.6 — 9 — — — —69.8 187.8 2.7 — 10 — — 2.4 — 65.4 151 2.3 0.949 11 — — — — 83.9 189.32.3 — 12 — — 2.1 — 67.3 175.4 2.6 0.969 *VYD means vinylidene. ⁺GPCvalues were not corrected for hexene content.

The branching index, g′(vis) is plotted against the % hexene in FIG. 1.

Example 2: Comparative Comparative Catalysts

General Preparation of SMAO-948:

Silica gel used was DAVISON™ 948, (W. R. Grace & Co., Houston, Tex.)calcined at 600° C. under a stream of nitrogen. To a slurry of silicagel (50 g) in toluene (100 ml) was slowly added methyl alumoxane (MAO,58 g, 30 wt % in toluene, Albemarle, Baton Rouge, La.) with stirring.The MAO used was not stripped of TMA and had about 15 wt % TMA. Thereaction mixture was heated to 90° C. for 2 hours, cooled, filtered, anddried in vacuo to yield a free-flowing solid.

Catalyst C-1: (CpMe₄)(CpPr)ZrCl₂

The (CpMe₄)(CpPr)ZrCl₂ catalyst was purchased from Boulder Scientific(Longmont, Colo.) and used as received. The catalyst may be representedby the structure C-1 in Table 2A.

SMAO-948 (50 g) was slurried in toluene (250 mls) at ambient temperatureand reacted with (CpMe₄)(CpPr)ZrCl₂ (0.36 g) for 3 hours. The solidcatalyst was filtered and dried in vacuo to yield a free-flowing solid.

Catalyst C-2: (CpMe₄)(CpBz)ZrCl₂

The (CpMe₄)(CpBz)ZrCl₂ catalyst was purchased from Boulder Scientificand used as received. The catalyst may be represented by the structureC-2 in Table 2A.

SMAO-948 (40 g) was slurried in toluene (150 mls) at ambient temperatureand reacted with (CpMe₄)(CpBz)ZrCl₂ (0.33 g) for 12 hours. The solidcatalyst was filtered and dried in vacuo to yield a free-flowing solid.

Catalyst C-3: Me₂Si(CpMe₄)(CpBz)ZrCl₂

Sodium cyclopentadiene (50 mls, Aldrich, 2.0 M in THF) was furtherdiluted with 200 mls THF and reacted with benzyl bromide (30 g, Aldrich)for 2 hours. The volatiles were removed and the crude reaction mixtureextracted with hexane (50 ml), filtered and the filtrate reduced to anoil. The crude product was Kugelrohr-distilled at maximum vacuum and thedistillate from 60° C. to 70° C. was collected. All was dissolvedimmediately in 100 ml hexane and deprotonated with nBuLi. The whitesolid product, Cp(Bz)Li, was collected on a glass frit (7.5 g). CpBzLi(2.3 g) was reacted with CpMe₄HSiMe₂C1 (3.0 g, Aldrich) which had beendissolved in THF (40 ml). After 30 minutes the volatiles were removedand the reaction re-dissolved in Et₂O (60 ml) and deprotonated withexcess nBuLi. The volatiles were removed after 12 hours and the soliddilithio salt washed with hexane, slurried in Et₂O (50 ml) and reactedwith ZrCl₄ (2.7 g). The crude reaction was filtered to yield an orangefiltrate which was reduced to an oil. The oil was stirred with hexane toyield an orange solid (0.6 g). ¹H NMR (250 MHz, C₆D₆) δ ppm; 7.1-7.0(m), 6.75 (m), 5.48 (m), 5.24 (m), 4.28 (s), 2.12 (s), 2.07 (s), 1.75(s), 1.68 (s), 0.39 (s), 0.30 (s). The metallocene compound may berepresented by the structure C-3 in Table 2A.

SMAO-948 (10 g) was slurried in toluene (30 mls) at ambient temperatureand reacted with Me₂Si(CpMe₄)(CpBz)ZrCl₂ (0.19 g) for 12 hours. Thesolid catalyst was filtered, washed with pentane (40 ml) and dried invacuo to yield a free-flowing light yellow solid.

Catalyst C-4: Me₂Si(Flu)(CpMe₄)ZrCl₂

Fluorene (42 g, Aldrich) was slurried in Et₂O (300 ml) and deprotonatedwith 1 equivalent nBuLi overnight. The orange solid was collected,washed with hexane, and dried in vacuo (35 g). Fluorenyl lithium (17 g)was dissolved in THF (200 ml) and reacted with CpMe₄H—SiMe₂C1 (30.4 g,Aldrich). After 2 hours the volatiles were removed and the crudeextracted with CH₂Cl₂ (2×60 ml). The extracts were reduced and 30 mlhexane were added and the solution cooled to recrystallize the neutralligand. A white solid was collected, dissolved in THF (100 ml) anddeprotonated with nBuLi (30 ml, 10 M in hexane). After 12 hours thedilithio ligand had fallen out of solution and was collected and washedwith hexane. All of the dilithio ligand (8.5 g) was slurried in Et₂O(100 ml) and reacted with ZrCl₄ (5.6 g). The solid product wascollected, washed with CH₂Cl₂ (50 ml) and dried to yield a yellow-orangesolid (9.4 g). The Me₂Si(Flu)(CpMe₄)ZrCl₂ product is extremely insolublein most solvents except THF in which it decomposes, and is representedby the structure C-4 in Table 2A. ¹H NMR (250 MHz, C₆D₆) δ ppm; 1.81(s), 1.78 (s), 0.88 (s).

SMAO-948 (10 g) was slurried in toluene (30 mls) at ambient temperatureand reacted with Me₂Si(Flu)(CpMe₄)ZrCl₂ (0.19 g) for 12 hours. The solidcatalyst was filtered, washed with hexane (40 ml) and dried in vacuo toyield a free-flowing pink solid.

Catalyst C-5: Me₂Si(n-propylCp)(Cp*)ZrCl₂

SMAO-948 (11 g) was slurried in toluene (30 mls) at ambient temperatureand reacted with Me₂Si(n-propylCp)(CpMe₄)ZrCl₂, represented by thestructure C-5 in Table 2A, (0.167 g, synthesized as in U.S. Pat. No.7,829,495), for 12 hours. The solid catalyst was filtered and dried invacuo to yield a free-flowing yellow solid.

Catalyst C-6: (Me₂Ind)₂HfCl₂

(Me₂Ind)₂HfCl₂ was purchased from Boulder Scientific, and used asreceived. (Me₂Ind)₂HfCl₂ is represented by the structure C-6 in Table2A.

SMAO-948 (10 g) was slurried in toluene 20 mls at ambient temperatureand reacted with (Me₂Ind)₂HfCl₂ (0.167 g) for 12 hours. The solidcatalyst was filtered and dried in vacuo to yield a free-flowing whitesolid.

Catalyst C-7: (CpMe₃Pr)(CpMe₄)ZrCl₂

CpMe₃(nPr)HLi was made as described in U.S. Pat. No. 6,025,512. CpMe₄HZrCl₃ was purchased from Strem Chemicals (Newburyport, Mass.).

CpMe₃(nPr)HLi (1.4 g, where nPr is n-propyl) was slurried in Et₂O (100ml) and reacted with CpMe₃ HZrCl₃ (3.0 g) for 12 hours at roomtemperature. The volatiles were removed and the crude reaction mixtureextracted with CH₂Cl₂ (60 ml), filtered through a glass frit and thefiltrate reduced to yield an off-white solid (3.1 g). The metallocenecompound may be represented by the structure C-7 in Table 2A. ¹H NMR(250 MHz, C₆D₆) δ ppm; 5.3 (s), 5.27 (s), 2.62 (m), 2.08 (s), 2.0 (s),1.8 (s), 1.75 (s), 1.73 (s), 1.3 (m), 0.89 (t).

SMAO-948 (7 g) was slurried in toluene (20 mls) at ambient temperatureand reacted with (CpMe₃Pr)(CpMe₄)ZrCl₂ (0.12 g) for 12 hours. The solidcatalyst was filtered and dried in vacuo to yield a free-flowing solid.

These MAO-activated supported metallocene compounds were run in slurrypolymerization. The structures are shown in Table 2A, below.

TABLE 2A COMPARATIVE SUPPORTED METALLOCENE COMPOUNDS SupportedMetallocene Compound Structure C-1

C-2

C-3

C-4

C-5

C-6

C-7

General Polymerization

Into a 1 L stainless steel autoclave reactor was added scavenger (TIBAL,as a hexane solution, Table 2B below) followed by 500 mls of isobutane.Ethylene was added (180 psi) and the reactor was heated to 80° C. withstirring rate set at 750 rpm. The supported catalyst system was thenadded by a short nitrogen purge through a small stainless steel bombattached securely to the reactor. Ethylene was maintained at the initialpressure throughout the polymerization. The polymerization was allowedto proceed for a set time at which time the reactor was cooled andexcess pressure vented into the hood. The solid resin was transferredinto an appropriate glass vessel and dried at 80° C. in a vacuum ovenfor at least 2 hours. The yields and resin characterization arepresented in Table 2C.

TABLE 2B REACTOR CONDITIONS FOR COMPARATIVE EXAMPLES TIBAL, Cat.Activity Slurry Metallocene 1.0M, Temp. Time, Yield, (g pol./ run #compound mls (° C.) min g g cat.) 13A C-1 0.15 80 30 55.26 526.7 13B C-10.15 80 30 67.35 666.8 14A C-2 0.15 80 30 54.05 530.4 14B C-2 0.15 80 3052.91 519.2 15A C-3 0.15 80 30 131.19 1360.89 15B C-3 0.15 80 30 134.071330.27 16A C-4 0.15 80 30 47.69 476.9 16B C-4 0.15 80 30 53.17 555.0017A C-5 0.15 80 30 166.04 1685.68 17B C-5 0.15 80 30 193.38 1974.25 18C-6 0.15 80 60 19.52 195.00 19 C-7 0.15 80 30 14.03 280.60

TABLE 2C POLYMER DATA FROM COMPARATIVE RUNS Mw, ×10³ Mn, ×10³ MWD, Mz,×10³ methyl Mn, ×10³ VYL¹/ VYD²/ Other/ g/mol g/mol (GPC/ g/mol groupsg/mol 1000 1000 1000 Run # (GPC) (GPC) GPC) (GPC) per 1000 C % VYL¹ ¹HNMR carbons carbons carbons 13A — — 0.95 — 0.90 17.39 60.87 0.04 0 0.1913B — — 0.95 — 0.90 0.00 73.68 0.00 0 0.19 14A 226.41 75.77 2.99 509.000.60 14.29 100.00 0.02 0 0.12 14B 218.24 67.43 3.24 507.58 0.60 22.22155.56 0.02 0 0.07 15A 60.68  9.34 6.49 644.37 1.80 30.95 33.33 0.13 00.29 15B — — — — 1.80 35.90 35.90 0.14 0 0.25 16A 237.81 63.90 3.72597.98 0.40 77.78 155.56 0.07 0 0.02 16B 232.40 66.67 3.49 560.70 0.4088.89 155.56 0.08 0 0.01 17A 48.18 18.17 2.65  87.36 1.70 28.57 40.000.10 0 0.25 17B 47.22 14.03 3.36  88.08 1.80 25.00 35.00 0.10 0 0.3 18275.24 102.67  2.68 559.47 0.60 31.25 87.50 0.05 0.02 0.09 19 272.1289.15 3.05 586.97 2.30 16.22 37.84 0.06 0 0.31 ¹VYL means Vinyl ²VYDmeans Vinylidene

Example 3 (Comparative) Catalysts Used

General Preparation of SMAO-948:

Silica gel used was DAVISON™ 948, (W. R. Grace & Co., Houston, Tex.)calcined at 600° C. under a stream of nitrogen. To a slurry of silicagel (50 g) in toluene (100 ml) was slowly added methyl alumoxane (MAO,58 g, 30 wt % in toluene, Albemarle, Baton Rouge, La.) with stirring.The MAO used was not stripped of TMA. The reaction mixture was heated to90° C. for 2 hours, cooled, filtered and dried in vacuo to yield afree-flowing solid.

Catalyst C-9

SMAO-948 (10 g) was slurried in toluene (30 mls) at ambient temperatureand reacted with [Me₂Si(Flu)(CpMe₄)]ZrCl₂ (0.19 g) for 12 hrs. The solidcatalyst was filtered, washed with hexane (40 ml) and dried in vacuo toyield a free-flowing pink solid.

The metallocene compound is represented by the following structure:

Catalyst C-10

SMAO-948 (5.0 g) was slurried in toluene (30 mls) at ambient temperatureand reacted with [Me₂Si(3-n-propylCpMe₃)(Flu)]ZrCl₂ (0.108 g) for 2 hrs.The solid catalyst was filtered, washed with hexane (40 ml) and dried invacuo to yield a free-flowing red-orange solid.

The metallocene compound is represented by the following structure:

General Polymerization

Into a 1 L stainless steel autoclave reactor was charged 400 mL ofhexane. Then 20 mL 1-hexene was added to the reactor. TIBAL (0.5 mL) wasadded as solution in 2 mL of toluene. Ethylene was added (125 psi) andthe reactor was heated to 85° C. with stirring rate set at 1280 rpm. Thesupported catalyst system (18.9 mg) was then added by a short nitrogenpurge, followed by a 100 mL hexane wash, through a small stainless steelbomb attached securely to the reactor. Ethylene was maintained at theinitial pressure throughout the polymerization. The polymerization wasallowed to proceed for thirty minutes at which time the reactor wascooled and excess pressure vented into the hood. The solid resin wastransferred into a glass vessel and dried at 80° C. in a vacuum oven forat least 2 hours. The yields and resin characterization are alsopresented in Table 3.

TABLE 3 REACTOR CONDITIONS AND POLYMER ANALYSIS FOR COMPARATIVE EXAMPLESRun # 1 2 Catalyst C-9 C-10 Amount of catalyst (mg) 18.9 36.3 Hexene(mL) 20 20 Ethylene (psig) 125 125 Ethylene (MPa) 0.86 0.86 Temperature(° C.) 85 85 Time (mins) 30 30 Yield (g) 5.5 4.8 Polymer AnalysisVinylene (¹H NMR), mols 0.01 0.01 Vinyl (¹H NMR), mols 0.17 0.14Vinylidene (¹H NMR), mols 0.02 0.01 % Vinyls 85 87 Mn (¹H NMR) (g/mol)70,000 88,000

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text, provided however that anypriority document not named in the initially filed application or filingdocuments is NOT incorporated by reference herein. As is apparent fromthe foregoing general description and the specific embodiments, whileforms of the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including” for purposes of Australian law.Likewise, “comprising” encompasses the terms “consisting essentiallyof,” “is,” and “consisting of” and anyplace “comprising” is used“consisting essentially of,” “is,” or “consisting of” may be substitutedtherefor.

We claim:
 1. A process to produce polyethylene comprising: (a)contacting ethylene with a supported metallocene catalyst system;wherein the supported catalyst system comprises: (i) a support material;(ii) an alumoxane activator having from about 1 wt % to about 14 wt %trimethylaluminum, based on the weight of the alumoxane activator; (iii)a metallocene compound represented by the formula:

wherein T is Si or Ge; each R^(A) is a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl group; each R^(B) is, independently, H or a C₁to C₈ substituted or unsubstituted hydrocarbyl group, or a grouprepresented by the formula —CH₂R^(x); wherein R^(x) is a C₁ to C₂₀substituted or unsubstituted hydrocarbyl group, provided that at leastone R^(B) is methyl or a group represented by the formula —CH₂R^(x);each R^(C) is, independently, H or a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl group; each A is independently selected fromthe group consisting of C₁ to C₂₀ substituted or unsubstitutedhydrocarbyl groups, hydrides, amides, amines, alkoxides, sulfides,phosphides, halides, dienes, phosphines, and ethers, and two A groupscan form a cyclic structure including aromatic, partially saturated, orsaturated cyclic or fused ring system; each X is, independently,hydrogen, halogen or a substituted or unsubstituted C₁ to C₂₀hydrocarbyl, and two X groups can form a cyclic structure includingaromatic, partially saturated, or saturated cyclic or fused ring system;further provided that any of adjacent R^(A), R^(B), and/or R^(C) groupsmay form a fused ring or multicenter fused ring systems, where the ringsmay be substituted or unsubstituted, and may be aromatic, partiallyunsaturated, or unsaturated; (b) obtaining a vinyl terminatedpolyethylene having: (i) at least 60% allyl chain ends, based on totalunsaturations; (ii) a molecular weight distribution of less than orequal to 4.0; and (iii) an Mn (¹HNMR) of at least 20,000 g/mol.
 2. Theprocess of claim 1, wherein the polyethylene is an ethylene polymerhaving less than 2 wt % of a C₃ to C₄₀ alphaolefin comonomer.
 3. Theprocess of claim 2, wherein the vinyl terminated polyethylene has atleast 95% allyl chain ends, based on total unsaturations.
 4. The processof claim 2, wherein the vinyl terminated polyethylene has a molecularweight distribution of less than or equal to 3.5.
 5. The process ofclaim 1, wherein the vinyl terminated polyethylene comprises 0 wt % of aC₃ to C₄₀ alphaolefin comonomer.
 6. The process of claim 1, wherein thevinyl terminated polyethylene 2 to about 20 wt % of a C₃ to C₄₀alphaolefin comonomer.
 7. The process of claim 6, wherein the vinylterminated polyethylene has at least 75 wt % allyl chain ends, based ontotal unsaturations.
 8. The process of claim 1, wherein the vinylterminated polyethylene has an Mn (GPC)/Mn (¹HNMR) in the range of fromabout 0.8 to about 1.2.
 9. The process of claim 1, wherein the vinylterminated polyethylene has an Mn (GPC)/Mn (¹HNMR) in the range of fromabout 0.9 to about 1.1.
 10. The process of claim 1, wherein 0 wt % ofhydrogen is used in the polymerization.
 11. The process of claim 1,wherein the group represented by the formula —CH₂R^(x) is selected fromthe group consisting of ethyl, n-propyl, n-butyl, sec-butyl, and benzylgroups.
 12. The process of claim 1, wherein R^(A) is methyl.
 13. Theprocess of claim 1, wherein R^(B) and/or R^(A) or R^(C) fuse to form asubstituted or unsubstituted indene or a fluorene.
 14. The process ofclaim 1, wherein the catalyst is represented by the following structure:

wherein each R^(B) is, independently, H or a C₁ to C₈ substituted orunsubstituted hydrocarbyl group, or a group represented by the formula—CH₂R^(x); wherein R^(x) is a C₁ to C₂₀ substituted or unsubstitutedhydrocarbyl group, provided that at least one R^(B) is methyl or a grouprepresented by the formula —CH₂R^(x).
 15. The process of claim 1,wherein the metallocene compound is represented by the followingstructure:


16. The process of claim 1, wherein the metallocene compound is one ormore of: Me₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂;Me₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂; Me₂Si(3-n-butylCpMe₃)(C₁₃H₈)ZrCl₂;Me₂Si(3-n-butylCpMe₃)(C₁₃H₈)ZrMe₂; Me₂Si(3-benzylCpMe₃)(C₁₃H₈)ZrCl₂;Me₂Si(3-benzylCpMe₃)(C₁₃H₈)ZrMe₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(C₁₃H₈)ZrCl₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(C₁₃H₈)ZrMe₂;Me₂Ge(3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂; Me₂Ge(3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;Et₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂; Et₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;(Hexyl)₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂;(Hexyl)₂Si(3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;[(C₃H₆)Si](3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂;[(C₃H₆)Si](3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂;[(C₄H₈)Si](3-n-propylCpMe₃)(C₁₃H₈)ZrCl₂;[(C₄H₈)Si](3-n-propylCpMe₃)(C₁₃H₈)ZrMe₂; Me₂Si(CpMe₄)(C₁₃H₈)ZrCl₂;Me₂Si(CpMe₄)(C₁₃H₈)ZrMe₂; Me₂Ge(CpMe₄)(C₁₃H₈)ZrCl₂;Me₂Ge(CpMe₄)(C₁₃H₈)ZrMe₂; Et₂Si(CpMe₄)(C₁₃H₈)ZrCl₂;Et₂Si(CpMe₄)(C₁₃H₈)ZrMe₂; (Hexyl)₂Si(CpMe₄)(C₁₃H₈)ZrCl₂;(Hexyl)₂Si(CpMe₄)(C₁₃H₈)ZrMe₂; [(C₃H₆)Si](CpMe₄)(C₁₃H₈)ZrCl₂;[(C₃H₆)Si](CpMe₄)(C₁₃H₈)ZrMe₂; [(C₄H₈)Si](CpMe₄)(C₁₃H₈)ZrCl₂;[(C₄H₈)Si](CpMe₄)(C₁₃H₈)ZrMe₂; Me₂Si(3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Si(3-n-butylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Si(3-benzylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Ge(3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Et₂Si(3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;(Hexyl)₂Si(3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;[(C₃H₆)Si](3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;[(C₄H₈)Si](3-n-propylCpMe₃)(2,3-Me₂C₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Me₂Si(CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Me₂Ge(CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Et₂Si(CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;(Hexyl)₂Si(CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;[(C₃H₆)Si](CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;[(C₃H₆)Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;[(C₃H₆)Si](CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;[(C₃H₆)Si](CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;[(C₃H₆)Si](CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;[(C₄H₈)Si](CpMe₄)(2-methyl,3-n-propylC₉H₄)ZrCl₂;[(C₄H₈)Si(CpMe₄)(2-methyl,3-n-butylC₉H₄)ZrCl₂;[(C₄H₈)Si](CpMe₄)(2-methyl,3-benzylC₉H₄)ZrCl₂;[(C₄H₈)Si](CpMe₄)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;[(C₄H₈)Si](CpMe₄)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Me₂Si(3-n-propylCpMe₃)(CpMe₄)ZrCl₂; Me₂Si(3-n-propylCpMe₃)(CpMe₄)ZrMe₂;Me₂Si(3-n-butylCpMe₃)(CpMe₄)ZrCl₂; Me₂Si(3-n-butylCpMe₃)(CpMe₄)ZrMe₂;Me₂Si(3-benzylCpMe₃)(CpMe₄)ZrCl₂; Me₂Si(3-benzylCpMe₃)(CpMe₄)ZrMe₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(CpMe₄)ZrCl₂;Me₂Si(3-CH₂-cyclopropylCpMe₃)(CpMe₄)ZrMe₂;Me₂Ge(3-n-propylCpMe₃)(CpMe₄)ZrCl₂; Me₂Ge(3-n-propylCpMe₃)(CpMe₄)ZrMe₂;Et₂Si(3-n-propylCpMe₃)(CpMe₄)ZrCl₂; Et₂Si(3-n-propylCpMe₃)(CpMe₄)ZrMe₂;(Hexyl)₂Si(3-n-propylCpMe₃)(CpMe₄)ZrCl₂;(Hexyl)₂Si(3-n-propylCpMe₃)(CpMe₄)ZrMe₂;[(C₃H₆)Si](3-n-propylCpMe₃)(CpMe₄)ZrCl₂;[(C₃H₆)Si](3-n-propylCpMe₃)(CpMe₄)ZrMe₂;[(C₄H₈)Si](3-n-propylCpMe₃)(CpMe₄)ZrCl₂;[(C₄H₈)Si](3-n-propylCpMe₃)(CpMe₄)ZrMe₂;rac-Me₂Si(2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-Me₂Si(2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-Me₂Si(2-Me,3-n-butylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-Me₂Si(2-Me,3-n-butylC₉H₄)₂ZrCl₂;rac-Me₂Si(2-Me,3-CH₂-cyclopropylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-Me₂Si(2-Me,3-CH₂-cyclopropylC₉H₄)₂ZrCl₂;rac-Me₂Ge(2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-Me₂Ge(2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-Et₂Si(2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;Et₂Si(2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-(Hexyl)₂Si(2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-(Hexyl)₂Si(2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-[(C₃H₆)Si](2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-[(C₃H₆)Si](2-Me,3-n-propylC₉H₄)₂ZrCl₂;rac-[(C₄H₈)Si](2-Me,3-n-propylC₉H₄)(2,3-Me₂C₉H₄)ZrCl₂;rac-[(C₄H₈)Si](2-Me,3-n-propylC₉H₄)₂ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Me₂Si(C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Me₂Ge(C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;Et₂Si(C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;(Hexyl)₂Si(C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;[(C₃H₆)Si](C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;[(C₃H₆)Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;[(C₃H₆)Si](C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;[(C₃H₆)Si](C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;[(C₃H₆)Si](C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂;[(C₄H₈)Si](C₁₃H₈)(2-methyl,3-n-propylC₉H₄)ZrCl₂;[(C₄H₈)Si(C₁₃H₈)(2-methyl,3-n-butylC₉H₄)ZrCl₂;[(C₄H₈)Si](C₁₃H₈)(2-methyl,3-benzylC₉H₄)ZrCl₂;[(C₄H₈)Si](C₁₃H₈)(2-methyl,3-sec-butylC₉H₄)ZrCl₂;[(C₄H₈)Si](C₁₃H₈)(2-methyl,3-CH₂-cyclopropylC₉H₄)ZrCl₂; and thezirconium dimethyl analogs of the above dichloride metallocenecompounds, wherein the Cl groups on the Zr are preplaced with CH₃groups; wherein Me is methyl, Et is ethyl, C₉H₄ is an indenyl group;C₁₃H₈ is a fluorenyl group, [(C₃H₆)Si] is silacyclobutyl bridge, and[(C₄H₈)Si] is silacyclopentyl bridge.
 17. The process of claim 1,wherein the support material is SiO₂, Al₂O₃, or SiO₂/Al₂O₃.
 18. Theprocess of claim 1, wherein the alumoxane activator is analkylalumoxane.
 19. The process of claim 1, wherein the alumoxaneactivator is methylalumoxane.
 20. The process of claim 1, wherein thealumoxane activator comprises from about 0.5 to about 13 wt %trimethylaluminum, based on total aluminum.
 21. The process of claim 1,wherein the alumoxane activator comprises from about 1.0 to about 12 wt% trimethylaluminum, based on total aluminum.
 22. The process of claim2, wherein the polyethylene has at least 98% allyl chain ends, based ontotal unsaturations.
 23. The process of claim 1, wherein the contactingstep (a) takes place at a temperature in the range of about 40° C. toabout 150° C.
 24. The process of claim 1, wherein the contacting step(a) takes place at a pressure in the range of from about 0.55 MPa toabout 2.4 MPa.
 25. The process of claim 1, wherein the polyethylene isin the form of free-flowing, discrete particles.
 26. The process ofclaim 1, wherein the polyethylene has a g′(vis) greater than 0.90. 27.The process of claim 1, wherein the polyethylene has an Mn (¹H NMR) ofless than 125,000 g/mol.
 28. A supported catalyst system comprising: (i)a support material; (ii) an alumoxane activator having from about 1 wt %to about 14 wt. % trimethylaluminum, based on the weight of thealumoxane activator; and (iii) a metallocene compound represented by theformula:

wherein T is Si or Ge; each R^(A) is a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl group; each R^(B) is, independently, H or a C₁to C₈ substituted or unsubstituted hydrocarbyl group, or a grouprepresented by the formula —CH₂R^(x); wherein R^(x) is a C₁ to C₂₀substituted or unsubstituted hydrocarbyl group, provided that at leastone R^(B) is methyl or a group represented by the formula —CH₂R^(x);each R^(C) is, independently, H or a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl group; each A is independently selected fromthe group consisting of C₁ to C₂₀ substituted or unsubstitutedhydrocarbyl groups, hydrides, amides, amines, alkoxides, sulfides,phosphides, halides, dienes, phosphines, and ethers, and two A groupscan form a cyclic structure including aromatic, partially saturated, orsaturated cyclic or fused ring system; each X is, independently,hydrogen, halogen or a substituted or unsubstituted C₁ to C₂₀hydrocarbyl, and two X groups can form a cyclic structure includingaromatic, partially saturated, or saturated cyclic or fused ring system;and further provided that any of adjacent R^(A), R^(B), and/or R^(C)groups may form a fused ring or multicenter fused ring systems, wherethe rings may be substituted or unsubstituted, and may be aromatic,partially unsaturated, or unsaturated.
 29. The supported catalyst systemof claim 28, further comprising one or more of triethylaluminum,tri-isobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, dibutyl zinc, and diethyl zinc.
 30. The catalystsystem of claim 28, wherein the metallocene compound is represented bythe following structure:

wherein each R^(B) is, independently, H or a C₁ to C₈ substituted orunsubstituted hydrocarbyl group, or a group represented by the formula—CH₂R^(x); wherein R^(x) is a C₁ to C₂₀ substituted or unsubstitutedhydrocarbyl group, provided that at least one R^(B) is methyl or a grouprepresented by the formula —CH₂R^(x).
 31. A vinyl terminatedpolyethylene having: (a) at least 60% allyl chain ends, based on totalunsaturations; (b) a molecular weight distribution of less than or equalto 4.0; (c) a g′vis) of greater than 0.95; and (d) an Mn (¹HNMR) of atleast 20,000 g/mol.
 32. A reaction product of the vinyl terminatedpolyethylene of claim 31 and a modifying agent, wherein the reactionproduct is a functionalized polyethylene having: (i) at least 50%modified groups; (ii) a molecular weight distribution of less than orequal to 4.0; and (iii) a g′(vis) of greater than 0.95.
 33. A fuel orlubricant comprising the functionalized polyethylene of claim 32.